Biochar Aggregate Particles

ABSTRACT

Biochar aggregate particles are provided that are less than 5 mm and are comprised of biochar fines that are less than 1 mm and a binding agent. The binding agent may be clay, starch, a lignin, a polymer and/or a lipid. The biochar aggregate particles may also include additives and/or surfactants. The biochar fines may further be treated with a surfactant solution, a vacuum, ultrasonics or infused with any number of additives.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/423,563, filed Feb. 2, 2017, titled BIOCHAR AGGREGATE PARTICLES,which applications claims priority to U.S. Provisional PatentApplication Ser. No. 62/290,026, filed on Feb. 2, 2016, titled BIOCHARAGGREGATE PARTICLES and U.S. Provisional Patent Application Ser. No.62/293,160, filed on Feb. 9, 2016, titled BIOCHARS FOR USE IN COMPOSTS;this application is a continuation-in-part of U.S. patent applicationSer. No. 15/973,191, filed May 7, 2018, titled BIOCHAR FOR USE WITHANIMALS, which application is a divisional of U.S. patent applicationSer. No. 15/419,976, filed on Jan. 30, 2017, titled BIOCHAR FOR USE WITHANIMALS (now U.S. Pat. No. 9,980,912), which application claims priorityto U.S. Provisional Patent Application Ser. No. 62/288,068, filed Jan.28, 2016, titled BIOCHAR FOR USE WITH ANIMALS, U.S. Provisional PatentApplication Ser. No. 62/293,160, filed on Feb. 9, 2016, titled BIOCHARSFOR USE IN COMPOSTS and U.S. Provisional Patent Application Ser. No.62/344,865 filed on Jun. 2, 2016 titled MINERAL SOLUBILIZINGMICROORGANISMS INFUSED BIOCHARS; this application is also acontinuation-in-part of U.S. patent application Ser. No. 16/238,995,filed Jan. 3, 2019, titled BIOCHAR AS A MICROBIAL CARRIER, which is acontinuation of U.S. patent application Ser. No. 15/393,214, filed onDec. 28, 2016, titled BIOCHAR AS A MICROBIAL CARRIER (now U.S. Pat. No.10,173,937) and which is a continuation of U.S. patent application Ser.No. 15/393,176, filed on Dec. 28, 2016, titled ADDITIVE INFUSED BIOCHAR(now U.S. Pat. No. 10,118,870), both of which claim priority to U.S.Provisional Patent Application Ser. No. 62/271,486 filed on Dec. 28,2015 titled ADDITIVE INFUSED BIOCHARS; this application is also acontinuation-in-part of U.S. patent application Ser. No. 16/406,986,filed on May 8, 2019, titled ENHANCED BIOCHAR, which is a continuationof U.S. patent application Ser. No. 15/792,486, filed on Oct. 24, 2017,titled ENHANCED BIOCHAR, which is a continuation of U.S. patentapplication Ser. No. 15/156,256, filed on May 16, 2016, titled ENHANCEDBIOCHAR (now U.S. Pat. No. 9,809,502), which claims priority to U.S.Provisional Patent Application No. 62/162,219, filed on May 15, 2015,titled ENHANCED BIOCHAR; this application is also a continuation-in-partof U.S. patent application Ser. No. 16/035,177, filed Jul. 13, 2018,titled BIOCHARS AND BIOCHAR TREATMENT PROCESSES, which is a divisionalof U.S. patent application Ser. No. 15/213,122, filed Jul. 18, 2016,titled BIOCHARS AND BIOCHAR TREATMENT PROCESSES (now U.S. Pat. No.10,023,503), which is a divisional of U.S. patent application Ser. No.14/873,053 filed on Oct. 1, 2015, titled BIOCHARS AND BIOCHAR TREATMENTPROCESSES, (now U.S. Pat. No. 10,252,951) which claims priority to U.S.Provisional Patent Application No. 62/058,445, filed on Oct. 1, 2014,titled METHODS, MATERIALS AND APPLICATIONS FOR CONTROLLED POROSITY ANDRELEASE STRUCTURES AND APPLICATIONS and U.S. Provisional PatentApplication No. 62/058,472, filed on Oct. 1, 2014, titled HIGH ADDITIVERETENTION BIOCHARS, METHODS AND APPLICATIONS.

FIELD OF INVENTION

The invention relates to a biochar product and methods of producing abiochar aggregate particle.

BACKGROUND

Biochar has been known for many years as a soil enhancer. It containshighly porous, high carbon content material similar to the type of verydark, fertile anthropogenic soil found in the Amazon Basin known asTerra Preta. Terra Preta has very high charcoal content and is made froma mixture of charcoal, bone, manure, among other substances. Biochar iscreated by the pyrolysis of biomass, which generally involves heatingand/or burning of organic matter, in a reduced oxygen environment, at apredetermined rate. Such heating and/or burning is stopped when thematter reaches a charcoal like stage. The highly porous material ofbiochar is perfectly suited to host beneficial microbes, retainnutrients, hold water, and act as a delivery system for a range ofbeneficial compounds suited to specific applications.

During the production of biochar, large portions of biochar fines ordust particles are created. Along with the loss of useful product, thesedust particles can cause problematic, or even hazardous conditions forbiochar manufacturing, packaging and in application, including in usethrough agricultural application equipment, in animal feed, or inapplication to compost. The various particle size distributions createdduring biochar manufacturing lead to distribution and applicationproblems with equipment and cause the necessity of sizing equipment andcostly capital expenditures. The low density of the biochar fines anddust particles also makes mixing of growth enhancers such as fertilizersor microbes difficult as it allows for settling, separation, anddistribution problems.

Given the known benefits of biochar, a need remains for: (i) a means toproduce biochar in such a way that it has consistent granular particlesizes and distributions and can meet application needs in commercialagriculture, animal feed or maintenance, and composting using standardequipment and (ii) a method to utilize residual biochar dust or biocharfines to create a product with consistent size and physical/chemicalproperties that can be uniformly distributed in large and small scaleapplications to have the highest positive impact in its applicationincluding but not limited to agriculture, animal feed or maintenance,and composting.

SUMMARY

The present invention relates to a method for producing biocharaggregate particles, including, but not limited to agglomerates,extrudates, pellets, or granules, from biochar using starch or otherbinding material and/or additives to ease application, enhance soilhealth, and increase water retention in the soil.

The method includes producing a biochar aggregate particle that maycontain biochar, or a mixture of biochar, binders, fillers, and otheradditives such as microbial products, bacteria, plant nutrients,minerals, agricultural chemicals, fertilizers or animal vitamins,medications, or supplements.

In one example, the method includes, collecting treated and/or untreatedbiochar particles, mixing said biochar particles with water and one ormore binders, such as a starch, polymer, clay, or lignin, to create aslurry, filter pressing or de-watering the slurry to create a paste andextruding the paste through an extruder and creating biochar aggregateparticles. Optionally, additives can be mixed with the slurry or paste.If collecting treated biochar particles, the particles may be treated inadvance, for example pH adjusted or treated to remove deleterioussubstances.

When extruding the paste, the paste may be cut into desired lengthpieces and dried. In certain applications, depending upon the extruder,the cutting of the extrudate can be done in conjunction with theextrusion process. Through this process, a specific sized, dust free,biochar aggregate particle is created that can be easily used inagricultural distribution equipment.

Using biochar aggregate particles allows for better application in boththe industrial and individual sectors by allowing for the utilization ofdiverse processing and distribution equipment. For example, theapplication of biochar aggregate particles into soil results in moreconsistently fuller plants with unvarying vitality and longevity thatcan ultimately be maintained with less water.

Other devices, apparatus, systems, methods, features and advantages ofthe invention are or will become apparent to one with skill in the artupon examination of the following figures and detailed description. Itis intended that all such additional systems, methods, features andadvantages be included within this description, be within the scope ofthe invention, and be protected by the accompanying claims.

BRIEF DESCRIPTION OF THE FIGURES

The invention may be better understood by referring to the followingfigures. The components in the figures are not necessarily to scale,emphasis instead being placed upon illustrating the principles of theinvention.

FIG. 1 illustrates a cross-section of one example of a raw biocharparticle.

FIG. 2a is a SEM (10 KV×3.00K 10.0 μm) of pore morphology of treatedbiochar made from pine.

FIG. 2b is a SEM (10 KV×3.00K 10.0 μm) of pore morphology of treatedbiochar made from birch.

FIG. 2c is a SEM (10 KV×3.00K 10.0 μm) of pore morphology of treatedbiochar made from coconut shells.

FIG. 3 is a chart showing porosity distribution of various biochars.

FIG. 4 is a flow chart process diagram of one implementation of aprocess for treating the raw biochar in accordance with the invention.

FIG. 4a illustrates a schematic of one example of an implementation of abiochar treat processes that that includes washing, pH adjustment andmoisture adjustment.

FIG. 4b illustrates yet another example of an implementation of abiochar treatment processing that includes inoculation.

FIG. 5 is a schematic flow diagram of one example of a treatment systemfor use in accordance with the present invention.

FIG. 6 is a chart showing the water holding capacities of treatedbiochar as compared to raw biochar and sandy clay loam soil and ascompared to raw biochar and sunshine potting soil.

FIG. 7 illustrates the different water retention capacities of rawbiochar versus treated biochar measured gravimetrically.

FIG. 8 is a chart showing the retained water in vacuum impregnatedbiochar over other biochars after a seven week period.

FIG. 9 is a chart showing the weight loss of treated biochars versus rawbiochar samples when heated at varying temperatures using a TGA testingmethod.

FIG. 10 illustrates the plant available water in raw biochar, versustreated biochar and treated dried biochar.

FIG. 11 is a graph showing the pH of various starting biochars that weremade from different starting materials and pyrolysis processtemperatures.

FIG. 12 is a chart showing various pH ranges and germination for treatedbiochars.

FIG. 13 is a Thermogravimetric Analysis (TGA) plot showing themeasurement of water content, heavy organics and light organics in asample.

FIG. 14 is a chart showing the impact of treatment on pores sizes ofbiochar derived from coconut.

FIG. 15 is a chart showing the impact of treatment on pores sizes ofbiochar derived from pine.

FIG. 16 is a chart showing the measured hydrophobicity index rawbiochar, vacuum treated biochar and surfactant treated biochar.

FIG. 17 is a flow diagram showing one example of a method for infusingbiochar.

FIG. 18 illustrates the improved liquid content of biochar using vacuumimpregnation as against soaking the biochar in liquid.

FIG. 19a is a chart comparing total retained water of treated biocharafter soaking and after vacuum impregnation.

FIG. 19b is a chart comparing water on the surface, interstitially andin the pores of biochar after soaking and after vacuum impregnation.

FIG. 20 illustrates how the amount of water or other liquid in the poresof vacuum processed biochars can be increased varied based upon theapplied pressure.

FIG. 21 illustrates the effects of NPK impregnation of biochar onlettuce yield.

FIG. 22 is a chart showing nitrate release curves of treated biocharsinfused with nitrate fertilizer.

FIGS. 23 and 24 are images that show how different sized bacteria willfit in different biochar pore size structures.

FIG. 25 illustrates release rate data verse total pore volume data forboth coconut shell and pine based treated biochars inoculated with areleasable bacteria.

FIG. 26 is a chart comparing examples of biochars.

FIGS. 27a, 27b, 27c are charts comparing different examples of biochars.

FIG. 28 is a chart comparing shoot biomass when the biochar added to asoilless mix containing soybean seeds is treated with microbial productcontaining Bradyrhizobium japonicum, and when it is untreated.

FIG. 29 shows the comparison of root biomass in a treated verses anuntreated environment.

FIG. 30 is a chart comparing the nitrogen levels when the biochar isinoculated with the rhizobial inoculant verses when it is notinoculated.

FIG. 31 illustrates the three day release rates of water infused biocharcompared to other types of biochar.

FIG. 32a is a SEM (10 KV×3.00K 10.0 μm) of pore morphology of rawbiochar.

FIG. 32b is a SEM (10 KV×3.00K 10.0 μm) of pore morphology of rawbiochar of FIG. 32a after it has been infused with microbial species.

FIG. 32c is a SEM (10 KV×3.00K 10.0 μm) of a pore morphology of anotherexample of raw biochar of FIG. 17a after it has been infused withmicrobial species.

FIG. 33 contains charts illustrating improved results obtained throughthe use of biochars.

FIG. 34 is an example of carbon dioxide production captured as acontinuous gas bubble in BGB (left two tubes) and LTB (right two tubes)growth medium.

FIGS. 35 and 36 illustrate improved growth rates of colonies ofStreptomyces lydicus using biochars.

FIG. 37a is an image of biochar aggregate particles of the presentinvention made in the form pellets.

FIG. 37b is an image of biochar aggregate particles of the presentinvention made in the form an extrudates.

FIG. 37c is an image of the biochar aggregate particles made in the formof biochar sulfur prills.

FIG. 38 is a flow diagram of one example of a method for producingbiochar aggregate particles.

FIGS. 39a-f illustrates the effects of size and grinding on particlestructure of a biochar derived from a first biomass.

FIGS. 40a-f illustrates the effects of size and grinding on particlestructure of a biochar derived from a second biomass.

FIG. 41a shows the effect of size fraction on water holding capacity oftwo different biomass based treated biochars.

FIG. 41b shows the effect of size fraction on pH of two differentbiomass based treated biochars.

FIG. 41c shows the effect of size fraction on Cl− concentration of twodifferent biomass based treated biochars.

FIG. 41d shows the effect of size fraction on electrical conductivity oftwo different biomass based treated biochars.

FIG. 42 is a diagram illustrating one example of the workflow for a foodcomposting operation.

FIG. 43 is a chart showing the pH of compost as the percent of lacticacid increases.

FIG. 44 is a chart showing how pH is influenced in compost when mixinggreens, woods and foods.

FIG. 45 is a chart showing the impact on composting temperatures whentreated biochar is added to compost.

FIG. 46 is a chart showing the decrease of lactic acid production incompost by adding treated biochar.

FIG. 47 is a chart showing the increase in pH in compost by addingtreated biochar.

FIG. 48 is a chart showing the increase in oxygen levels in compost byadding treated biochar.

FIG. 49 is a chart showing the impact of the addition of both raw andtreated biochar in a CASP compost environment to volatile fatty acids(VFAs).

FIG. 50 is a chart showing the impact of the addition of both raw andtreated biochar in a CASP compost environment to NH₃ levels.

FIG. 51 is a chart showing the impact on volatile organic compounds(“VOC”) by adding treated and raw biochar to CASP compost.

FIG. 52 is a chart shows a test of evaporative water loss from controlcompost against blended treatments with raw or processed biochars at 1,3 and 5% by volume.

FIG. 53 is a chart showing the effect that the addition of treatedbiochar has on percent mass water loss in a CASP compost environment.

FIG. 54 is a chart showing in impact of the addition of the inoculatedbiochar to compost on microbial abundance.

FIG. 55 is a chart showing in impact of the addition of the inoculatedbiochar to compost on VOCs.

FIG. 56 is a chart showing in impact of the addition of the inoculatedbiochar to compost on NH₃.

FIG. 57 is chart illustrating biochar capacity to absorb Cadmium.

DESCRIPTION OF THE INVENTION

As illustrated in the attached figures, the present invention relates toa method for producing biochar aggregate particles that can be used inprocessing and distribution equipment for improved industrialapplication including but not limited to agriculture, animal health andmaintenance, and compositing, when increased density or uniform particlesize, composition or distribution is preferred or required in order toachieve the highest positive impact in its application.

For the purposes of this application, prior treatment of the rawbiochar, as described below, is not required as part of the productionof the biochar aggregate particles. However, often treatment ispreferred as the properties of the raw biochar can be modified tosignificantly increase the biochar's ability to retain water and/ornutrients while also, in many cases, creating an environment beneficialto microorganisms. The processing of the biochar can also ensure thatthe pH of biochar used in the present application is suitable for itsapplication, which has been a challenge for raw biochars. In certainapplication, it may be desirable to produce the biochar aggregateparticles from treated biochars or the fines of treated biochars.

Biochars derived from different biomass or produced with differingparameters, such as higher or lower pyrolysis temperature or variationsin residence time, will have different physical and chemical propertiesand can behave quite differently in different applications. For example,some chars will have a fairly uniform granular particle size and shapewith a high density and relatively high crush strength that flows well,while others will have a low density and a low crush strength whichmeans they breakdown easily creating many fines and dust particles andwill also lead to poor flow characteristics. But these biochars withpoor particle characteristics might be more economic or due to theirother physical or chemical characteristics more effective in a specificapplication. Thus, turning these biochars into an aggregate of thepresent invention, allows them to be more useful and effective throughstandard processing and application equipment.

A good example of aggregate need is when a biochar will be used as acomponent of an animal feed or be mixed with a granular fertilizer priorto application in agriculture. Mixing of particles that aresignificantly different in shape, size, or density will generally leadto segregation during shipping, handling, or application. Thusaggregating the biochar into a similar particle shape, size, or densityof the rest of the mixture, say fertilizer or animal feed pellet, willallow for a uniform mix and rate to be achieved when fed to the animalor applied to the soil.

Currently biochar has mostly been a scientific curiosity, not found inwide spread use or large scale commercial applications, and instead hasbeen relegated to small niche applications. It is, however, known, thatbiochar, having certain characteristics can host beneficial microbes,retain nutrients and supplements, hold liquids for agriculturalapplications. Accordingly, these same characteristics of biochar can beharnessed for other application such as composting, remediation, oranimal maintenance, care and feeding.

For purposes of this application, the term “biochar” shall be given itsbroadest possible meaning and shall include any solid carbonaceousmaterials obtained from the pyrolysis, torrefaction, gasification or anyother thermal and/or chemical conversion of a biomass. For purposes ofthis application, the solid carbonaceous material may include, but notbe limited to, BMF char disclosed and taught by U.S. Pat. No. 8,317,891,which is incorporated into this application by reference. Pyrolysis isgenerally defined as a thermochemical decomposition of organic materialat elevated temperatures in the absence of, or with reduced levels ofoxygen. When the biochar is referred to as “treated” or undergoes“treatment,” it shall mean raw, pyrolyzed biochar that has undergoneadditional physical, biological, and/or chemical processing.

As used herein, unless specified otherwise, the terms “carbonaceous”,“carbon based”, “carbon containing”, and similar such terms are to begiven their broadest possible meaning, and would include materialscontaining carbon in various states, crystallinities, forms andcompounds.

As used herein, unless stated otherwise, room temperature is 25° C. And,standard temperature and pressure is 25° C. and 1 atmosphere. Unlessstated otherwise, generally, the term “about” is meant to encompass avariance or range of ±10%, the experimental or instrument errorassociated with obtaining the stated value, and preferably the larger ofthese.

A. Biochars

Typically, biochars include porous carbonaceous materials, such ascharcoal, that are used as soil amendments or other suitableapplications. Biochar most commonly is created by pyrolysis of abiomass. In addition to the benefits to plant growth, yield and quality,etc.; biochar provides the benefit of reducing carbon dioxide (CO₂) inthe atmosphere by serving as a method of carbon sequestration. Thus,biochar has the potential to help mitigate climate change, via carbonsequestration. However, to accomplish this important, yet ancillarybenefit, to any meaningful extent, the use of biochar in agriculturalapplications must become widely accepted, e.g., ubiquitous.Unfortunately, because of the prior failings in the biochar arts, thishas not occurred. It is believed that with the solutions of the presentinvention may this level of use of biochar be achieved; and moreimportantly, yet heretofore unobtainable, realize the benefit ofsignificant carbon dioxide sequestration.

In general, one advantage of putting biochar in soil includes long termcarbon sequestration. It is theorized that as worldwide carbon dioxideemissions continue to mount, benefits may be obtained by, controlling,mitigating and reducing the amount of carbon dioxide in the atmosphereand the oceans. It is further theorized that increased carbon dioxideemissions are associated with the increasing industrial development ofdeveloping nations, and are also associated with the increase in theworld's population. In addition to requiring more energy, the increasingworld population will require more food. Thus, rising carbon dioxideemissions can be viewed as linked to the increasing use of naturalresources by an ever increasing global population. As some suggest, thislarger population brings with it further demands on food productionrequirements. Biochar uniquely addresses both of these issues byproviding an effective carbon sink, e.g., carbon sequestration agent, aswell as, an agent for improving and increasing agricultural output. Inparticular, biochar is unique in its ability to increase agriculturalproduction, without increasing carbon dioxide emission, and preferablyreducing the amount of carbon dioxide in the atmosphere. However, asdiscussed above, this unique ability of biochar has not been realized,or seen, because of the inherent problems and failings of prior biocharsincluding, for example, high pH, phytotoxicity due to high metalscontent and/or residual organics, and dramatic product inconsistencies.

Biochar can be made from basically any source of carbon, for example,from hydrocarbons (e.g., petroleum based materials, coal, lignite, peat)and from a biomass (e.g., woods, hardwoods, softwoods, waste paper,coconut shell, manure, chaff, food waste, etc.). Combinations andvariations of these starting materials, and various and differentmembers of each group of starting materials can be, and are, used. Thus,the large number of vastly different starting materials leads tobiochars having different properties.

Many different pyrolysis or carbonization processes can be, and areused, to create biochars. In general, these processes involve heatingthe starting material under positive pressure, reduced pressure, vacuum,inert atmosphere, or flowing inert atmosphere, through one or moreheating cycles where the temperature of the material is generallybrought above about 400° C., and can range from about 300° C. to about900° C. The percentage of residual carbon formed and several otherinitial properties are strong functions of the temperature and timehistory of the heating cycles. In general, the faster the heating rateand the higher the final temperature the lower the char yield.Conversely, in general, the slower the heating rate or the lower thefinal temperature the greater the char yield. The higher finaltemperatures also lead to modifying the char properties by changing theinorganic mineral matter compositions, which in turn, modify the charproperties. Ramp, or heating rates, hold times, cooling profiles,pressures, flow rates, and type of atmosphere can all be controlled, andtypically are different from one biochar supplier to the next. Thesedifferences potentially lead to a biochar having different properties,further framing the substantial nature of one of the problems that thepresent inventions address and solve. Generally, in carbonization mostof the non-carbon elements, hydrogen and oxygen are first removed ingaseous form by the pyrolytic decomposition of the starting materials,e.g., the biomass. The free carbon atoms group or arrange intocrystallographic formations known as elementary graphite crystallites.Typically, at this point the mutual arrangement of the crystallite isirregular, so that free interstices exist between them. Thus, pyrolysisinvolves thermal decomposition of carbonaceous material, e.g., thebiomass, eliminating non-carbon species, and producing a fixed carbonstructure.

As noted above, raw or untreated biochar is generally produced bysubjecting biomass to either a uniform or varying pyrolysis temperature(e.g., 300° C. to 550° C. to 750° C. or more) for a prescribed period oftime in a reduced oxygen environment. This process may either occurquickly, with high reactor temperature and short residence times, slowlywith lower reactor temperatures and longer residence times, or anywherein between. To achieve better results, the biomass from which the charis obtained may be first stripped of debris, such as bark, leaves andsmall branches, although this is not necessary. The biomass may furtherinclude feedstock to help adjust the pH and particle size distributionin the resulting raw biochar. In some applications, it is desirous tohave biomass that is fresh, less than six months old, and with an ashcontent of less than 3%. Further, by using biochar derived fromdifferent biomass, e.g., pine, oak, hickory, birch and coconut shellsfrom different regions, and understanding the starting properties of theraw biochar, the treatment methods can be tailored to ultimately yield atreated biochar with predetermined, predictable physical and chemicalproperties.

In general, biochar particles can have a very wide variety of particlesizes and distributions, usually reflecting the sizes occurring in theinput biomass. Additionally, biochar can be ground or crushed afterpyrolysis to further modify the particle sizes. Typically, foragricultural uses, biochars with consistent, predictable particle sizesare more desirable. By way of example, the biochar particles can haveparticle sizes as shown or measured in Table 1 below. When referring toa batch having ¼ inch particles, the batch would have particles thatwill pass through a 3 mesh sieve, but will not pass through (i.e., arecaught by or sit atop) a 4 mesh sieve.

TABLE 1 U.S. Mesh Microns Millimeters (i.e., mesh) Inches (μm) (mm) 30.2650 6730 6.370 4 0.1870 4760 4.760 5 0.1570 4000 4.000 6 0.1320 33603.360 7 0.1110 2830 2.830 8 0.0937 2380 2.380 10 0.0787 2000 2.000 120.0661 1680 1.680 14 0.0555 1410 1.410 16 0.0469 1190 1.190 18 0.03941000 1.000 20 0.0331 841 0.841 25 0.0280 707 0.707 30 0.0232 595 0.59535 0.0197 500 0.500 40 0.0165 400 0.400 45 0.0138 354 0.354 50 0.0117297 0.297 60 0.0098 250 0.250 70 0.0083 210 0.210 80 0.0070 177 0.177100 0.0059 149 0.149 120 0.0049 125 0.125 140 0.0041 105 0.105 1700.0035 88 0.088 200 0.0029 74 0.074 230 0.0024 63 0.063 270 0.0021 530.053 325 0.0017 44 0.044 400 0.0015 37 0.037

For most applications, it is desirable to use biochar particles havingparticle sizes from about 3/4 mesh to about 60/70 mesh, about 4/5 meshto about 20/25 mesh, or about 4/5 mesh to about 30/35 mesh. It beingunderstood that the desired mesh size, and mesh size distribution canvary depending upon a particular application for which the biochar isintended.

FIG. 1 illustrates a cross-section of one example of a raw biocharparticle. As illustrated in FIG. 1, a biochar particle 100 is a porousstructure that has an outer surface 100 a and a pore structure 101formed within the biochar particle 100. As used herein, unless specifiedotherwise, the terms “porosity”, “porous”, “porous structure”, and“porous morphology” and similar such terms are to be given theirbroadest possible meaning, and would include materials having openpores, closed pores, and combinations of open and closed pores, andwould also include macropores, mesopores, and micropores andcombinations, variations and continuums of these morphologies. Unlessspecified otherwise, the term “pore volume” is the total volume occupiedby the pores in a particle or collection of particles; the term“inter-particle void volume” is the volume that exists between acollection of particle; the term “solid volume or volume of solid means”is the volume occupied by the solid material and does not include anyfree volume that may be associated with the pore or inter-particle voidvolumes; and the term “bulk volume” is the apparent volume of thematerial including the particle volume, the inter-particle void volume,and the internal pore volume.

The pore structure 101 forms an opening 121 in the outer surface 100 aof the biochar particle 100. The pore structure 101 has a macropore 102,which has a macropore surface 102 a, and which surface 102 a has anarea, i.e., the macropore surface area. (In this diagram only a singlemicropore is shown. If multiple micropores are present than the sum oftheir surface areas would equal the total macropore surface area for thebiochar particle.) From the macropore 102, several mesopores 105, 106,107, 108 and 109 are present, each having its respective surfaces 105 a,106 a, 107 a, 108 a and 109 a. Thus, each mesopore has its respectivesurface area; and the sum of all mesopore surface areas would be thetotal mesopore surface area for the particle. From the mesopores, e.g.,107, there are several micropores 110, 111, 112, 113, 114, 115, 116,117, 118, 119 and 120, each having its respective surfaces 110 a, 111 a,112 a, 113 a, 114 a, 115 a, 116 a, 117 a, 118 a, 119 a and 120 a. Thus,each micropore has its respective surface area and the sum of allmicropore surface areas would be the total micropore surface area forthe particle. The sum of the macropore surface area, the mesoporesurface area and the micropore surface area would be the total poresurface area for the particle.

Macropores are typically defined as pores having a diameter greater than300 nm, mesopores are typically defined as diameter from about 1-300 nm,and micropores are typically defined as diameter of less than about 1nm, and combinations, variations and continuums of these morphologies.The macropores each have a macropore volume, and the sum of thesevolumes would be the total macropore volume. The mesopores each have amesopore volume, and the sum of these volumes would be the totalmesopore volume. The micropores each have a micropore volume, and thesum of these volumes would be the total micropore volume. The sum of themacropore volume, the mesopore volume and the micropore volume would bethe total pore volume for the particle.

Additionally, the total pore surface area, volume, mesopore volume,etc., for a batch of biochar would be the actual, estimated, andpreferably calculated sum of all of the individual properties for eachbiochar particle in the batch.

It should be understood that the pore morphology in a biochar particlemay have several of the pore structures shown, it may have mesoporesopening to the particle surface, it may have micropores opening toparticle surface, it may have micropores opening to macropore surfaces,or other combinations or variations of interrelationship and structurebetween the pores. It should further be understood that the poremorphology may be a continuum, where moving inwardly along the pore fromthe surface of the particle, the pore transitions, e.g., its diameterbecomes smaller, from a macropore, to a mesopore, to a micropore, e.g.,macropore 102 to mesopore 109 to micropore 114.

In general, the biochars have porosities that can range from 0.2 cm³/cm³to about 0.8 cm³/cm³ and more preferably about 0.2 cm³/cm³ to about 0.5cm³/cm³. (Unless stated otherwise, porosity is provided as the ratio ofthe total pore volumes (the sum of the micro+meso+macro pore volumes) tothe solid volume of the biochar. Porosity of the biochar particles canbe determined, or measured, by measuring the micro-, meso-, and macropore volumes, the bulk volume, and the inter particle volumes todetermine the solid volume by difference. The porosity is thencalculated from the total pore volume and the solid volume.

As noted above, the use of different biomass potentially leads tobiochars having different properties, including, but not limited todifferent pore structures. By way of example, FIGS. 2A, 2B and 2Cillustrate Scanning Electron Microscope (“SEM”) images of various typesof treated biochars showing the different nature of their poremorphology. FIG. 2A is biochar derived from pine. FIG. 2B is biocharderived from birch. FIG. 2C is biochar derived from coconut shells.

The surface area and pore volume for each type of pore, e.g., macro-,meso- and micro- can be determined by direct measurement using CO₂adsorption for micro-, N₂ adsorption for meso- and macro pores andstandard analytical surface area analyzers and methods, for example,particle analyzers such as Micrometrics instruments for meso- and micropores and impregnation capacity for macro pore volume. Mercuryporosimetry, which measures the macroporosity by applying pressure to asample immersed in mercury at a pressure calibrated for the minimum porediameter to be measured, may also be used to measure pore volume.

The total micropore volume can be from about 2% to about 25% of thetotal pore volume. The total mesopore volume can be from about 4% toabout 35% of the total pore volume. The total macropore volume can befrom about 40% to about 95% of the total pore volume. By way of example,FIG. 3 shows a bar chart setting out examples of the pore volumes forsample biochars made from peach pits 201, juniper wood 202, a first hardwood 203, a second hard wood 204, fir and pine waste wood 205, a firstpine 206, a second pine 207, birch 208 and coconut shells 209.

As explained further below, treatment can increase usable pore volumesand, among other things, remove obstructions in the pores, which leadsto increased retention properties and promotes further performancecharacteristics of the biochar. Knowing the properties of the startingraw biochar, one can treat the biochar to produce controlled,predictable and optimal resulting physical and chemical properties.

B. Treatment

The rationale for treating the biochar after pyrolysis is that given thelarge pore volume and large surface are of the biochars, it is mostefficient to make significant changes in the physical and chemicalproperties of the biochar by treating both the internal and externalsurfaces and internal pore volume of the char. Testing has demonstratedthat if the biochar is treated, at least partially, in a manner thatcauses the forced infusion and/or diffusion of liquids into and/or outof the biochar pores (through mechanical, physical, or chemical means),certain properties of the biochar can be altered or improved over andabove simply contacting these liquids with the biochar. By knowing theproperties of the raw biochar and the optimal desired properties of thetreated biochar, the raw biochar can then be treated in a manner thatresults in the treated biochar having controlled optimized properties.

For purposes of this application, treating and/or washing the biochar inaccordance with the present invention involves more than a simple washor soak, which generally only impacts the exterior surfaces and a smallpercentage of the interior surface area. “Washing” or “treating” inaccordance with the present invention, and as used below, involvestreatment of the biochar in a manner that causes the forced, acceleratedor assisted infusion and/or diffusion of liquids and/or additivitiesinto and/or out of the biochar pores (through mechanical, physical, orchemical means) such that certain properties of the biochar can bealtered or improved over and above simply contacting these liquids withthe biochar or so that treatment becomes more efficient or rapid from atime standpoint over simple contact or immersion.

In particular, effective treatment processes can mitigate deleteriouspore surface properties, remove undesirable substances from poresurfaces or volume, and impact anywhere from between 10% to 99% or moreof pore surface area of a biochar particle. By modifying the usable poresurfaces through treatment and removing deleterious substances from thepore volume, the treated biochars can exhibit a greater capacity toretain water and/or other nutrients as well as being more suitablehabitats for some forms of microbial life. Through the use of treatedbiochars, agricultural applications can realize increased moisturecontrol, increased nutrient retention, reduced water usage, reducedwater requirements, reduced runoff or leaching, increased nutrientefficiency, reduced nutrient usage, increased yields, increased yieldswith lower water requirements and/or nutrient requirements, increases inbeneficial microbial life, improved performance and/or shelf life forinoculated bacteria, and any combination and variation of these andother benefits.

Treatment further allows the biochar to be modified to possess certainknown properties that enhance the benefits received from the use ofbiochar. While the selection of feedstock, raw biochar and/or pyrolysisconditions under which the biochar was manufactured can make treatmentprocesses less cumbersome, more efficient and further controlled,treatment processes can be utilized that provide for the biochar to havedesired and generally sustainable resulting properties regardless of thebiochar source or pyrolysis conditions. As explained further below,treatment can (i) repurpose problematic biochars, (ii) handle changingbiochar material sources, e.g., seasonal and regional changes in thesource of biomass, (iii) provide for custom features and functions ofbiochar for particular soils, regions or agricultural purposes; (iv)increase the retention properties of biochar, (v) provide for largevolumes of biochar having desired and predictable properties, (vi)provide for biochar having custom properties, (vii) handle differencesin biochar caused by variations in pyrolysis conditions or manufacturingof the “raw” biochar; and (viii) address the majority, if not all, ofthe problems that have, prior to the present invention, stifled thelarge scale adoption and use of biochars.

Treatment can wash both the interior and exterior pore surfaces, removeharmful chemicals, introduce beneficial substances, and alter certainproperties of the biochar and the pore surfaces and volumes. This is instark contrast to simple washing which generally only impacts theexterior surfaces and a small percentage of the interior surface area.Treatment can further be used to coat substantially all of the biocharpore surfaces with a surface modifying agent or impregnate the porevolume with additives or treatment to provide a predetermined feature tothe biochar, e.g., surface charge and charge density, surface speciesand distribution, targeted nutrient addition, magnetic modifications,root growth facilitator, and water absorptivity and water retentionproperties. Just as importantly, treatment can also be used to removeundesirable substances from the biochar, such as dioxins or other toxinseither through physical removal or through chemical reactions causingneutralization.

FIG. 4 is a schematic flow diagram of one example treatment process 400for use in accordance with the present invention. As illustrated, thetreatment process 400 starts with raw biochar 402 that may be subjectedto one or more reactors or treatment processes prior to bagging 420 thetreated biochar for resale. For example, 404 represents reactor 1, whichmay be used to treat the biochar. The treatment may be a simple waterwash or may be an acid wash used for the purpose of altering the pH ofthe raw biochar particles 402. The treatment may also contain asurfactant or detergent to aid the penetration of the treatment solutioninto the pores of the biochar. The treatment may optionally be heated,cooled, or may be used at ambient temperature or any combination of thethree. For some applications, depending upon the properties of the rawbiochar, a water and/or acid/alkaline wash 404 (the latter for pHadjustment) may be the only necessary treatment prior to bagging thebiochar 420. If, however, the moisture content of the biochar needs tobe adjusted, the treated biochar may then be put into a second reactor406 for purposes of reducing the moisture content in the washed biochar.From there, the treated and moisture adjusted biochar may be bagged 420.

Again, depending upon the starting characteristics of the raw biocharand the intended application for the resale product, further processingmay still be needed or desired. In this case, the treated moistureadjusted biochar may then be passed to a third reactor 408 forinoculation, which may include the impregnation of biochar withbeneficial additives, such as nutrients, bacteria, microbes, fertilizersor other additives. Thereafter, the inoculated biochar may be bagged420, or may be yet further processed, for example, in a fourth reactor410 to have further moisture removed from or added to the biochar.Further moisture adjustment may be accomplished by placing theinoculated biochar in a fourth moisture adjustment reactor 410 orcirculating the biochar back to a previous moisture adjustment reactor(e.g. reactor 406). Those skilled in the art will recognize that theordering in which the raw biochar is processed and certain processes maybe left out, depending on the properties of the starting raw biochar andthe desired application for the biochar. For example, the treatment andinoculation processes may be performed without the moisture adjustmentstep, inoculation processes may also be performed with or without anytreatment, pH adjustment or any moisture adjustment. All the processesmay be completed alone or in the conjunction with one or more of theothers.

For example, FIG. 4a illustrates a schematic of one example of animplementation of biochar processing that includes washing the pores andboth pH and moisture adjustment. FIG. 4b illustrates yet another exampleof an implementation of biochar processing that includes inoculation.

As illustrated in FIG. 4a , raw biochar 402 is placed into a reactor ortank 404. A washing or treatment liquid 403 is then added to a tank anda partial vacuum, using a vacuum pump, 405 is pulled on the tank. Thetreating or washing liquid 403 may be used to clean or wash the pores ofthe biochar 402 or adjust the chemical or physical properties of thesurface area or pore volume, such as pH level, usable pore volume, orVOC content, among other things. The vacuum can be applied after thetreatment liquid 403 is added or while the treatment liquid 403 isadded. Thereafter, the washed/adjusted biochar 410 may be moistureadjusted by vacuum exfiltration 406 to pull the extra liquid from thewashed/moisture adjusted biochar 410 or may be placed in a centrifuge407, heated or subjected to pressure gradient changes (e.g., blowingair) for moisture adjustment. The moisture adjusted biochar 412 may thenbe bagged or subject to further treatment. Any excess liquids 415collected from the moisture adjustment step may be disposed of orrecycled, as desired. Optionally, biochar fines may be collected fromthe excess liquids 415 for further processing, for example, to create aslurry, cakes, or biochar extrudates.

Optionally, rather than using a vacuum pump 405, a positive pressurepump may be used to apply positive pressure to the tank 404. In somesituations, applying positive pressure to the tank may also function toforce or accelerate the washing or treating liquid 403 into the pores ofthe biochar 402. Any change in pressure in the tank 404 or across thesurface of the biochar could facilitate the exchange of gas and/ormoisture into and out of the pores of the biochar with the washing ortreating liquid 403 in the tank. Accordingly, changing the pressure inthe tank and across the surface of the biochar, whether positive ornegative, is within the scope of this invention.

As illustrated FIG. 4b , the washed/adjusted biochar 410 or thewashed/adjusted and moisture adjusted biochar 412 may be further treatedby inoculating or impregnating the pores of the biochar with an additive425. The biochar 410, 412 placed back in a reactor 401, an additivesolution 425 is placed in the reactor 401 and a vacuum, using a vacuumpump, 405 is applied on the tank. Again, the vacuum can be applied afterthe additive solution 425 is added to the tank or while the additivesolution 425 is being added to the tank. Thereafter, the washed,adjusted and inoculated biochar 428 can be bagged. Alternatively, iffurther moisture adjustment is required, the biochar can be furthermoisture adjusted by vacuum filtration 406 to pull the extra liquid fromthe washed/moisture adjusted biochar 410 or may be placed in acentrifuge 407 for moisture adjustment. The resulting biochar 430 canthen be bagged. Any excess liquids 415 collected from the moistureadjustment step may be disposed of or recycled, as desired. Optionally,biochar particulates or “fines” which easily are suspended in liquid maybe collected from the excess liquids 415 for further processing, forexample, to create a slurry, biochar extrudates, or merely a biocharproduct of a consistently smaller particle size. As described above,both processes of the FIGS. 4a and 4b can be performed with a surfactantsolution in place of, or in conjunction with, the vacuum 405.

While known processes exist for the above described processes, researchassociated with the present invention has shown improvement and theability to better control the properties and characteristics of thebiochar if the processes are performed through the infusion anddiffusion of liquids into and out of the biochar pores. One suchtreatment process that can be used is vacuum impregnation and vacuumand/or centrifuge extraction. Another such treatment process that can beused is the addition of a surfactant to infused liquid, which infusedliquid may be optionally heated, cooled, or used at ambient temperatureor any combination of the three.

Since research associated with the present invention has identified whatphysical and chemical properties have the highest impact on plant growthand/or soil health, the treatment process can be geared to treatdifferent forms of raw biochar to achieve treated biochar propertiesknown to enhance these characteristics. For example, if the pH of thebiochar needs to be adjusted to enhance the raw biochar performanceproperties, the treatment may be the infusion of an acid solution intothe pores of the biochar using vacuum, surfactant, or other treatmentmeans. This treatment of pore infusion through, for example, the rapid,forced infusion of liquid into and out the pores of the biochar, hasfurther been proven to sustain the adjusted pH levels of the treatedbiochar for much longer periods than biochar that is simply immersed inan acid solution for the same period of time. By way of another example,if the moisture content needs to be adjusted, then excess liquid andother selected substances (e.g. chlorides, dioxins, and other chemicals,to include those previously deposited by treatment to catalyze orotherwise react with substances on the interior or exterior surfaces ofthe biochar) can be extracted from the pores using vacuum and/orcentrifuge extraction or by using various heating techniques. The abovedescribes a few examples of treatment that result in treated biocharhaving desired performance properties identified to enhance soil healthand plant life.

FIG. 5 illustrates one example of a system 500 that utilizes vacuumimpregnation to treat raw biochar. Generally, raw biochar particles, andpreferably a batch of biochar particles, are placed in a reactor, whichis connected to a vacuum pump, and a source of treating liquid (i.e.water or acidic/basis solution). When the valve to the reactor isclosed, the pressure in the reactor is reduced to values ranging from750 Torr to 400 Torr to 10 Torr or less. The biochar is maintained undervacuum (“vacuum hold time”) for anywhere from seconds to 1 minute to 10minutes, to 100 minutes, or possibly longer. By way of example, forabout a 500 pound batch of untreated biochar, a vacuum hold time of fromabout 1 to about 5 minutes can be used if the reactor is of sufficientsize and sufficient infiltrate is available to adjust the necessaryproperties. While under the vacuum the treating liquid may then beintroduced into the vacuum chamber containing the biochar.Alternatively, the treating liquid may be introduced into the vacuumchamber before the biochar is placed under a vacuum. Optionally,treatment may also include subjecting the biochar to elevatedtemperatures from ambient to about 250° C. or reduced temperatures toabout −25° C. or below, with the limiting factor being the temperatureand time at which the infiltrate can remain flowable as a liquid orsemi-liquid.

The infiltrate or treating liquid is drawn into the biochar pore, andpreferably drawn into the macropores and mesopores. Depending upon thespecific doses applied and pore structure of the biochar, the infiltratecan coat anywhere from 10% to 50% to 100% of the total macropore andmesopore surface area and can fill or coat anywhere from a portion tonearly all (10%-100%) of the total macropore and mesopore volume.

As described above, the treating liquid can be left in the biochar, withthe batch being a treated biochar batch ready for packaging, shipmentand use in an agricultural or other application. The treating liquid mayalso be removed through drying, subsequent vacuum processing,centrifugal force (e.g., cyclone drying machines or centrifuges), withthe batch being a treated biochar batch ready for packaging, shipmentand use in an agricultural application. A second, third or moreinfiltration, removal, infiltration and removal, and combinations andvariations of these may also be performed on the biochar with optionaldrying steps between infiltrations to remove residual liquid from andreintroduce gasses to the pore structure if needed. In any of thesestages the liquid may contain organic or inorganic surfactants to assistwith the penetration of the treating liquid.

As illustrated in FIG. 5, a system 500 for providing a biochar,preferably having predetermined and uniform properties. The system 500has a vacuum infiltration tank 501. The vacuum infiltration tank 501 hasan inlet line 503 that has a valve 504 that seals the inlet line 503. Inoperation, the starting biochar is added to vacuum infiltration tank 501as shown by arrow 540. Once the tank is filled with the startingbiochar, a vacuum is pulled on the tank, by a vacuum pump connected tovacuum line 506, which also has valve 507. The starting biochar is heldin the vacuum for a vacuum hold time. Infiltrate, as shown by arrow 548is added to the tank 501 by line 508 having valve 509. The infiltrate ismixed with the biochar in the tank 501 by agitator 502. The mixingprocess is done under vacuum for a period of time sufficient to have theinfiltrate fill the desired amount of pore volume, e.g., up to 100% ofthe macropores and mesopores.

Alternatively, the infiltrate may be added to the vacuum infiltrationtank 501 before vacuum is pulled on the tank. In this manner, infiltrateis added in the tank in an amount that can be impregnated into thebiochar. As the vacuum is pulled, the biochar is circulated in the tankto cause the infiltrate to fill the pore volume. To one skilled in theart, it should be clear that the agitation of the biochar during thisprocess can be performed through various means, such as a rotating tank,rotating agitator, pressure variation in the tank itself, or othermeans. Additionally, the biochar may be dried using conventional meansbefore even the first treatment. This optional pre-drying can removeliquid from the pores and in some situations may increase the efficiencyof impregnation due to pressure changes in the tank.

Pressure is then restored in the tank 501 and the infiltrated biochar isremoved, as shown by arrow 541, from the tank 501 to bin 512, by way ofa sealing gate 511 and removal line 510. The infiltrated biochar iscollected in bin 512, where it can be further processed in severaldifferent ways. The infiltrated biochar can be shipped for use as atreated biochar as shown by arrow 543. The infiltrated biochar can bereturned to the tank 501 (or a second infiltration tank). If returned tothe tank 501 the biochar can be processed with a second infiltrationstep, a vacuum drying step, a washing step, or combinations andvariations of these. The infiltrated biochar can be moved by conveyor514, as shown by arrow 542, to a drying apparatus 516, e.g., acentrifugal dryer or heater, where water, infiltrate or other liquid isremoved by way of line 517, and the dried biochar leaves the dryerthrough discharge line 518 as shown by arrow 545, and is collected inbin 519. The biochar is removed from the bin by discharge 520. Thebiochar may be shipped as a treated biochar for use in an agricultureapplication, as shown by arrow 547. The biochar may also be furtherprocessed, as shown by 546. Thus, the biochar could be returned to tank501 (or a second vacuum infiltration tank) for a further infiltrationstep. The drying step may be repeated either by returning the drybiochar to the drying apparatus 516, or by running the biochar through aseries of drying apparatus, until the predetermined dryness of thebiochar is obtained, e.g., between 50% to less than 1% moisture.

The system 500 is illustrative of the system, equipment and processesthat can be used for, and to carry out the present inventions. Variousother implementations and types of equipment can be used. The vacuuminfiltration tank can be a sealable off-axis rotating vessel, chamber ortank. It can have an internal agitator that also when reversed can movematerial out, empty it, (e.g., a vessel along the lines of a largecement truck, or ready mix truck, that can mix and move material out ofthe tank, without requiring the tank's orientation to be changed).Washing equipment may be added or utilized at various points in theprocess, or may be carried out in the vacuum tank, or drier, (e.g., washfluid added to biochar as it is placed into the drier for removal).Other steps, such as bagging, weighing, the mixing of the biochar withother materials, e.g., fertilized, peat, soil, etc. can be carried out.In all areas of the system referring to vacuum infiltration, optionallypositive pressure can be applied, if needed, to enhance the penetrationof the infiltrate or to assist with re-infusion of gaseous vapors intothe treated char. Additionally, where feasible, especially in positivepressure environments, the infiltrate may have soluble gasses addedwhich then can assist with removal of liquid from the pores, or gaseoustreatment of the pores upon equalization of pressure.

As noted above, the biochar may also be treated using a surfactant. Thesame or similar equipment used in the vacuum infiltration process can beused in the surfactant treatment process. Although it is not necessaryto apply a vacuum in the surfactant treatment process, the vacuuminfiltration tank or any other rotating vessel, chamber or tank can beused. In the surfactant treatment process, a surfactant, such as yuccaextract, is added to the infiltrate, e.g., acid wash or water. Thequantity of the surfactant added to the infiltrate may vary dependingupon the surfactant used. For example, organic yucca extract can beadded at a rate of between 0.1-20%, but more preferably 1-5% by volumeof the infiltrate. The infiltrate with surfactant is then mixed with thebiochar in a tumbler for several minutes, e.g., 3-5 minutes, withoutapplied vacuum. Optionally, a vacuum or positive pressure may be appliedwith the surfactant to improve efficiency, but is not necessary.Additionally, infiltrate to which the surfactant or detergent is addedmay be heated or may be ambient temperature or less. Similarly, themixture of the surfactant or detergent, as well as the char beingtreated may be heated, or may be ambient temperature, or less. Aftertumbling, excess free liquid can be removed in the same manner asdescribed above in connection with the vacuum infiltration process.Drying, also as described above in connection with the vacuuminfiltration process, is an optional additional step. Besides yuccaextract, a number of other surfactants may be used for surfactanttreatment, which include, but are not limited to, the following:nonionic types, such as, ethoxylated alcohols, phenols-lauryl alcoholethoxylates, Fatty acid esters-sorbitan, tween 20, amines,amides-imidazoles; anionic types, such as sulfonates-arylalkylsulfonates and sulfate-sodium dodecyl sulfate; cationic types, such asalkyl-amines or ammoniums-quaternary ammoniums; and amphoteric types,such as betaines-cocamidopropyl betaine.

Optionally, the biochar may also be treated by applying ultrasonics. Inthis treatment process, the biochar may be contacted with a treatingliquid that is agitated by ultrasonic waves. By agitating the treatingliquid, contaminants may be dislodged or removed from the biochar due tobulk motion of the fluid in and around the biocarbon, pressure changes,including cavitation in and around contaminants on the surface, as wellas pressure changes in or near pore openings (cavitation bubbles) andinternal pore cavitation.

In this manner, agitation will cause contaminants of many forms to bereleased from the internal and external structure of the biochar. Theagitation also encourages the exchange of water, gas, and other liquidswith the internal biochar structure. Contaminants are transported fromthe internal structure to the bulk liquid (treating fluid) resulting inbiochar with improved physical and chemical properties. Theeffectiveness of ultrasonic cleaning is tunable as bubble size andnumber is a function of frequency and power delivered by the transducerto the treating fluid

In one example, applying ultrasonic treatment, raw wood based biocharbetween 10 microns to 10 mm with moisture content from 0% to 90% may bemixed with a dilute mixture of acetic acid and water (together thetreating liquid) in a processing vessel that also translates the slurry(the biochar/treating liquid mixture). During translation, the slurrypasses near an ultrasonic transducer to enhance the interaction betweenthe fluid and biochar. The biochar may experience one or multiple washesof dilute acetic acid, water, or other treating fluids. The biochar mayalso make multiple passes by ultrasonic transducers to enhance physicaland chemical properties of the biochar. For example, once a large volumeof slurry is made, it can continuously pass an ultrasonic device and bedegassed and wetted to its maximum, at a rapid processing rate. Theslurry can also undergo a separation process in which the fluid andsolid biochar are separated at 60% effectiveness or greater.

Through ultrasonic treatment, the pH of the biochar, or other physicaland chemical properties may be adjusted and the mesopore and macroporesurfaces of the biochar may be cleaned and enhanced. Further, ultrasonictreatment can be used in combination with bulk mixing with water,solvents, additives (fertilizers, etc.), and other liquid basedchemicals to enhance the properties of the biochar. After treatment, thebiochar may be subject to moisture adjustment, further treatment and/orinoculation using any of the methods set forth above.

C. Benefits of Treatment

As illustrated above, the treatment process, whether using vacuum,surfactant or ultrasonic treatment, or a combination thereof, mayinclude two steps, which in certain applications, may be combined: (i)washing and (ii) inoculation of the pores with an additive. When thedesired additive is the same and that being inoculated into the pores,e.g., water, the step of washing the pores and inoculating the poreswith an additive may be combined.

While not exclusive, washing is generally done for one of threepurposes: (i) to modify the surface of the pore structure of the biochar(i.e., to allow for increased retention of liquids); (ii) to modify thepH of the biochar; and/or (iii) to remove undesired and potentiallyharmful compounds or gases.

1. Increases Water Holding Capacity/Water Retention Capacity

As demonstrated below, the treatment processes of the invention modifythe surfaces of the pore structure to provide enhanced functionality andto control the properties of the biochar to achieve consistent andpredicable performance. Using the above treatment processes, anywherefrom at least 10% of the total pore surface area up to 90% or more ofthe total pore surface area may be modified. In some implementations, itmay be possible to achieve modification of up to 99% or more of thetotal pore surface area of the biochar particle. Using the processes setforth above, such modification may be substantially and uniformlyachieved for an entire batch of treated biochar.

For example, it is believed that by treating the biochar as set forthabove, the hydrophilicity of the surface of the pores of the biochar ismodified, allowing for a greater water retention capacity. Further, bytreating the biochars as set forth above, gases and other substances arealso removed from the pores of the biochar particles, also contributingto the biochar particles' increased water holding capacity. Thus, theability of the biochar to retain liquids, whether water or additives insolution, is increased, which also increases the ability to load thebiochar particles with large volumes of inoculant, infiltrates and/oradditives.

A batch of biochar has a bulk density, which is defined as weight ingrams (g) per cm³ of loosely poured material that has or retains somefree space between the particles. The biochar particles in this batchwill also have a solid density, which is the weight in grams (g) per cm³of just particles, i.e., with the free space between the particlesremoved. The solid density includes the air space or free space that iscontained within the pores, but not the free space between particles.The actual density of the particles is the density of the material ingrams (g) per cm³ of material, which makes up the biochar particles,i.e., the solid material with pore volume removed.

In general, as bulk density increases the pore volume is expected todecrease. When the pore volume is macro or mesoporous, the ability ofthe material to hold infiltrate, e.g., inoculant is directlyproportional to the pore volume, thus it is also expected to decrease asbulk density increases. With the infiltration processes, the treatedbiochars can have impregnation capacities that are larger than could beobtained without infiltration, e.g., the treated biochars can readilyhave 30%, 40%, 50%, or most preferably, 60%-100% of their total porevolume filled with an infiltrate, e.g., an inoculant. The impregnationcapacity is the amount of a liquid that a biochar particle, or batch ofparticles, can absorb. The ability to make the pores surfacehydrophilic, and to infuse liquid deep into the pore structure throughthe application of positive or negative pressure and/or a surfactant,alone or in combination, provides the ability to obtain these highimpregnation capabilities. The treated biochars can have impregnationcapacities, i.e., the amount of infiltrate that a particle can hold on avolume held/total volume of a particle basis, that is greater than 0.2cm³/cm³ to 0.8 cm³/cm³. Resulting bulk densities of treated biochar canrange from 0.1-0.6 g/cm³ and sometimes preferably between 0.3-0.6 g/cm³and can have solid densities ranging from 0.2-1.2 g/cm³.

Accordingly, by using the treatment above, the water retention capacityof biochar can be greatly increased over the water retention capacitiesof various soil types and even raw biochar, thereby holding water and/ornutrients in the plant's root zone longer and ultimately reducing theamount of applied water (through irrigation, rainfall, or other means)needed by up to 50% or more. FIG. 6 is a chart showing the waterretention capacities of soils versus raw and treated biochar. The soilssampled are loam and sandy clay soil and a common commercialhorticultural mix. The charts show the retained water as a function oftime.

In chart A, the bottom line represents the retained water in the sandyclaim loam soil over time. The middle line represents the retained waterin the sandy clay soil with 20% by volume percent of unprocessed rawbiochar. The top line represents the retained water in the sandy clayloam soil with 20% by volume percent of treated biochar (adjusted andinoculated biochar). Chart B represents the same using a soillesspotting mix rather than sandy clay loam soil.

As illustrated in FIG. 7, testing showed a treated biochar had anincreased water retention capacity of approximately 1.5 times that ofthe raw biochar from the same feedstock. Similar results have been seenwith biochars derived from various feedstocks. With certain biochartypes, the water retention capacity of treated biochar could be as greatas three times that of raw biochar.

“Water holding capacity,” which may also be referred to as “WaterRetention Capacity,” is the amount of water that can be held bothinternally within the porous structure and in the interparticle voidspaces in a given batch of particles. While a summary of the method ofmeasure is provided above, a more specific method of measuring waterholding capacity/water retention capacity is measured by the followingprocedure: (i) drying a sample of material under temperatures of 105° C.for a period of 24 hours or using another scientifically acceptabletechnique to reduce the moisture content of the material to less than2%, less than 1%; and preferably less than 0.5% (ii) placing a measuredamount of dry material in a container; (iii) filling the containerhaving the measured amount of material with water such that the materialis completely immersed in the water; (iv) letting the water remain inthe container having the measured amount of material for at least tenminutes or treating the material in accordance with the invention byinfusing with water when the material is a treated biochar; (v) drainingthe water from the container until the water ceases to drain; (vi)weighing the material in the container (i.e., wet weight); (vii) againdrying the material by heating it under temperatures of 105° C. for aperiod of 24 hours or using another scientifically acceptable techniqueto reduce the moisture content of the material to less than 2% andpreferably less than 1%; and (viii) weighing the dry material again(i.e., dry weight) and, for purposes of a volumetric measure,determining the volume of the material.

Measured gravimetrically, the water holding/water retention capacity isdetermined by measuring the difference in weight of the material fromstep (vi) to step (viii) over the weight of the material from step(viii) (i.e., wet weight-dry weight/dry weight). FIG. 8 illustrates thedifferent water retention capacities of raw biochar versus treatedbiochar measured gravimetrically. As illustrated, water retentioncapacity of raw biochar can be between 100-200%, whereas treated biocharcan have water retention capacities measured gravimetrically between200-400%.

Water holding capacity can also be measured volumetrically andrepresented as a percent of the volume of water retained in the biocharafter gravitationally draining the excess water/volume of biochar Thevolume of water retained in the biochar after draining the water can bedetermined from the difference between the water added to the containerand water drained off the container or from the difference in the weightof the wet biochar from the weight of the dry biochar converted to avolumetric measurement. This percentage water holding capacity fortreated biochar may be 50-55 percent and above by volume.

Given biochar's increased water retention capacity, the application ofthe treated biochar and even the raw biochar can greatly assist with thereduction of water and/or nutrient application. It has been discoveredthat these same benefits can be imparted to agricultural growth.

Treated biochar of the present invention has also demonstrated theability to retain more water than raw biochar after exposure to theenvironment for defined periods of time. For purposes of thisapplication “remaining water content” can be defined as the total amountof water that remains held by the biochar after exposure to theenvironment for certain amount of time. Exposure to environment isexposure at ambient temperature and pressures. Under this definition,remaining water content can be measured by (i) creating a sample ofbiochar that has reached its maximum water holding capacity; (ii)determining the total water content by thermogravimetric analysis (H₂O(TGA)), as described above on a sample removed from the output of step(i) above, (iii) exposing the biochar in the remaining sample to theenvironment for a period of 2 weeks (15 days, 360 hrs.); (iv)determining the remaining water content by thermogravimetric analysis(H₂O (TGA)); and (v) normalizing the remaining (retained) water in mL to1 kg or 1 L biochar. The percentage of water remaining after exposurefor this two-week period can be calculated by the remaining watercontent of the biochar after the predetermined period over the watercontent of the biochar at the commencement of the two-week period. Usingthis test, treated biochar has shown to retain water at rates over 4×that of raw biochar. Testing has further demonstrated that the followingamount of water can remain in treated biochar after two weeks ofexposure to the environment: 100-650 mL/kg; 45-150 mL/L; 12-30 gal/ton;3-10 gal/yd³ after 360 hours (15 days) of exposure to the environment.In this manner, and as illustrated in FIG. 8, biochar treated with aprocess consistent with those described in this disclosure can increasethe amount of retained water in biochar about 3 times compared to othermethods even after seven weeks. In general, the more porous and thehigher the surface area of a given material, the higher the waterretention capacity. Further, it is theorized that by modifying thehydrophilicity/hydrophobicity of the pore surfaces, greater waterholding capacity and controlled release may be obtained. Thus, viewed asa weight percent, e.g., the weight of retained water to weight ofbiochar, examples of the present biochars can retain more than 5% oftheir weight, more than 10% of their weight, and more than 15% of theirweight, and even more than 50% of their weight compared to an averagesoil which may retain 2% or less, or between 100-600 ml/kg by weight ofbiochar.

Tests have also shown that treated biochars that show weight loss of >1%in the interval between 43-60° C. when analyzed by the ThermalGravimetric Analysis (TGA) (as described below) demonstrate greaterwater holding and content capacities over raw biochars. Weight lossof >5%-15% in the interval between 38-68° C. when analyzed by theThermal Gravimetric Analysis (TGA) using sequences of time andtemperature disclosed in the following paragraphs or others may also berealized. Weight percentage ranges may vary from between >1%-15% intemperature ranges between 38-68° C., or subsets thereof, to distinguishbetween treated biochar and raw biochar.

FIG. 9 is a chart 900 showing the weight loss of treated biochars 902versus raw biochar samples 904 when heated at varying temperatures usingthe TGA testing described below. As illustrated, the treated biochars902 continue to exhibit weight loss when heated between 40-60° C. whenanalyzed by the Thermal Gravimetric Analysis (TGA) (described below),whereas the weight loss in raw biochar 804 between the same temperatureranges levels off. Thus, testing demonstrates the presence of additionalmoisture content in treated biochars 902 versus raw biochars 904.

In particular, the treated biochars 902 exhibit substantial water losswhen heated in inert gas such as nitrogen following treatment. Moreparticularly, when heated for 25 minutes at each of the followingtemperatures 20, 30, 40, 50 and 60° C. the treated samples lose about5-% to 15% in the interval 43-60° C. and upward of 20-30% in theinterval between 38-68° C. The samples to determine the water content ofthe raw biochar were obtained by mixing a measured amount of biochar andwater, stirring the biochar and water for 2 minutes, draining off thewater, measuring moisture content and then subjecting the sample to TGA.The samples for the treated biochar were obtained by using the samemeasured amount of biochar as used in the raw biochar sample and usingtreatment process consistent with those described in this disclosure.The moisture content is then measured and the sample is subjected to TGAdescribed above.

The sequences of time and temperature conditions for evaluating theeffect of biochars heating in inert atmosphere is defined in thisapplication as the “Bontchev-Cheyne Test” (“BCT”). The BCT is run usingsamples obtained, as described above, and applying Thermal GravimetricAnalysis (TGA) carried out using a Hitachi STA 7200 analyzer undernitrogen flow at the rate of 110 mL/min. The biochar samples are heatedfor 25 minutes at each of the following temperatures: 20, 30, 40, 50 and60° C. The sample weights are measured at the end of each dwell step, atthe beginning and at the end of the experiment. The analyzer alsocontinually measures and records weight over time. Biochars treated witha process consistent with those described in this disclosure to enhancewater holding or retention capacities typically exhibit weight lossof >5% in the interval between 38-68° C., >1% in the interval between43-60° C. Biochars with greater water holding or retention capacitiescan exhibit >5% weight loss in the interval between 43-60° C. measuredusing the above described BCT.

Lastly, as illustrated in FIG. 10, plant available water is greatlyincreased in treated biochar over that of raw biochar. FIG. 10illustrates the plant available water in raw biochar, versus treatedbiochar and treated dried biochar and illustrates that treated biocharcan have a plant available water percent of greater than 35% by volume.

“Plant Available Water” is the amount of unbound water in a materialavailable for plants to uptake. This is calculated by subtracting thevolumetric water content at the permanent wilting point from thevolumetric water content at field capacity, which is the point when nowater is available for the plants. Field capacity is generally expressedas the bulk water content retained in at −33 J/kg (or −0.33 bar) ofhydraulic head or suction pressure. Permanent wilting point is generallyexpressed as the bulk water content retained at −1500 J/kg (or −15 bar)of hydraulic head or suction pressure. Methods for measuring plantavailable water are well-known in the industry and use pressure plateextractors, which are commercially available or can be built usingwell-known principles of operation.

2. Adjusts pH

With regard to treatment for pH adjustment, the above described vacuuminfiltration processes and/or surfactant treatment processes have theability to take raw biochars having detrimental or deleterious pHs andtransform those biochars into a treated biochar having pH that is in anoptimal range for most plant growth, and soil health. Turning to FIG.11, a graph 1100 is provided that shows the pH of various starting rawbiochars that were made from different starting materials and pyrolysisprocess temperatures, including coconut shells 1104, pistachio shells1101, corn at 500° C. 1105, corn at 900° C. 1102, bamboo 1103, mesquite1106, wood and coffee 1108, wood (Australia) 1109, various soft woods1110, 1111, 1112, 1113, 1114, 1115, 1116, 1117, red fir at 900° C. 1107,various grasses at 500° C. 1118, 1119, 1120, grass 1121, and grass at900° C. 1123. The treatment processes described in this disclosure, canbe used to alter the pH from the various undesirable pH levels and bringthe pH into the preferred, optimal range 1124 for most plant growth,soil health and combinations of these. FIG. 12 is a chart 1200 showingpercentage of germination for lettuce plants for particular pHs, and adesired germination range 1201. A control 1204 is compared with anoptimal pH range 1202, and a distribution 1203 of growth rates acrosspHs is shown.

If treated for pH adjustment, the treated biochar takes a few days aftertreatment for the pH to normalize. Once normalized, tests have proventhat pH altered biochar remains at a stable pH, typically the treatmentis used to lower the stable pH to below that of the raw biochar, for upto 12 months or more after treatment. Although in certain situations,the pH could be altered to be higher than the raw biochar when needed.

For example, the treatment process of the present invention can removeand/or neutralize inorganic compounds, such as the calcium hydroxide((CaOH)₂), potassium oxide (K₂OK₂OK₂O), magnesium oxide (MgO), magnesiumhydroxide (Mg(OH)₂), and many others that are formed during pyrolysis,and are fixed to the biochar pore surfaces. These inorganics, inparticular calcium hydroxide, adversely affect the biochar's pH, makingthe pH in some instances as high as 8.5, 9.5, 10.5 and 11.2. These highpH ranges are deleterious, detrimental to crops, and may kill oradversely affect the plants, sometimes rendering an entire field a loss.

The calcium hydroxide, and other inorganics, cannot readily and quicklybe removed by simple washing of the biochar, even in an acid bath. Itcannot be removed by drying the biochar, such as by heating orcentrifugal force. It is theorized that these techniques andmethodologies cannot reach or otherwise affect the various poresurfaces, e.g., macro-, meso- and micro- in any viable or efficaciousmanner; and thus cannot remove or otherwise neutralize the calciumhydroxide.

Upon modification of the pore surface area by removal and/orneutralization of deleterious substances, such as calcium hydroxide, thepH of the biochar can be reduced to the range of about pH 5 to about pH8, and more preferably from about pH 6.4 to about 7.2, and still morepreferably around 6.5 to 6.8, recognizing that other ranges and pHs arecontemplated and may prove useful, under specific environmental oragricultural situations or for other applications. Thus, the presenttreated biochars, particles, batches and both, have most, essentiallyall, and more preferably all, of their pore surfaces modified by theremoval, neutralization and both, of the calcium hydroxide that ispresent in the starting biochar material. These treated biochars havepHs in the range of about 5 to about 8, about 6.5 to about 7.5, about6.4 to about 7, and about 6.8. Prior to and before testing, biochar ispassed through a 2 mm sieve before pH is measured. All measurements aretaken according to Rajkovich et. al, Corn growth and nitrogen nutritionafter additions of biochars with varying properties to a temperate soil,Biol. Fertil. Soils (2011), from which the International BiocharInitiative (IBI) method is based.

There are a wide variety of tests, apparatus and equipment for making pHmeasurements. For example, and preferably when addressing the pH ofbiochar, batches, particles and pore surfaces of those particles, twoappropriates for measuring pH are the Test Method for the US CompostingCouncil (“TMCC”) 4.11-A and the pH Test Method promulgated by theInternational Biochar Initiative. The test method for the TMCC comprisesmixing biochar with distilled water in 1:5 [mass:volume] ratio, e.g., 50grams of biochar is added to 250 ml of pH 7.0±0.02 water and is stirredfor 10 minutes; the pH is then the measured pH of the slurry. The pHTest Method promulgated by the International Biochar Initiativecomprises 5 grams of biochar is added to 100 ml of water pH=7.0±0.02 andthe mixture is tumbled for 90 minutes; the pH of the slurry is measuredat the end of the 90 minutes of tumbling.

3. Removing/Neutralizing Deleterious Materials

Further, the treatment processes are capable of modifying the poresurfaces to remove or neutralize deleterious materials that areotherwise difficult, if not for all practical purpose, impossible tomitigate. For example, heavy metals, transition metals, sodium andphytotoxic organics, polycyclic aromatic hydrocarbons, volatile organiccompounds (VOCs), and perhaps other phytotoxins. Thus, by treating thebiochar in accordance with the treatment processes set forth anddescribed above, the resulting treated biochar has essentially all, andmore preferably all, of their pore surfaces modified by the removal,neutralization and both, of one or more deleterious, harmful, orpotentially harmful material that is present in the starting biocharmaterial.

For example, treatment can reduce the total percentage of residualorganic compounds (ROC), including both the percentage of heavy ROCs andpercentage of VOCs. Through treatment, the total ROC can be reduced to0-25% wt. %, percentage heavy ROC content can be reduced to 0-20% wt. %and VOC content can be reduced to less than 5% wt. %. For purposes ofthis application, “Residual organic compounds” (ROCs) are defined ascompounds that burn off during thermogravimetric analysis, as definedabove, between 150 degrees C. and 950 degrees C. Residual organiccompounds include, but are not limited to, phenols, polyaromatichydrocarbons, monoaromatic hydrocarbons, acids, alcohols, esters,ethers, ketones, sugars, alkanes and alkenes. Of the ROCs, those thatburn off using thermogravimetric analysis between 150 degrees C. and 550degrees are considered light organic compounds (volatiles or VOCs), andthose that burn off between 550 degrees C. and 950 degrees C. are heavyresidual organic compounds. It should be noted that there may be someinorganic compounds which also are burned off during TGA analysis inthese temperature ranges, but these are generally a very low percentageof the total emission and can be disregarded in the vast majority ofcases as slight variations. In any of these measurements, a gaschromatograph/mass spectrometer may be used if needed for higher degreesof precision.

The percent water, total organic compounds, total light organiccompounds (volatiles or VOC) and total heavy organic compounds, asreferenced in this application as contained in a biochar particle orparticles in a sample may all be measured by thermogravimetric analysis.Thermogravimetric analysis is performed by a Hitachi STA 7200 analyzeror similar piece of equipment under nitrogen flow at the rate of 110mL/min. The biochar samples are heated for predetermined periods oftime, e.g., 20 minutes, at a variety of temperatures between 100 and950° C. The sample weights are measured at the end of each dwell stepand at the beginning and at the end of the experiment. Thermogravimetricanalysis of a given sample indicating percentage water in a sample isdetermined by % mass loss measured between standard temperature and 150degrees C. Thermogravimetric analysis of a given sample indicatingpercentage of residual organic compounds is measured by percentage massloss sustained between 150 degrees C. and 950 degrees C.Thermogravimetric analysis of a given sample indicating percentage oflight organic compounds (volatiles) is measured by percentage mass losssustained between 150 degrees C. and 550 degrees C. Thermogravimetricanalysis of a given sample indicating percentage of heavy organiccompounds is measured by percentage mass loss sustained between 550degrees C. and 950 degrees C. FIG. 13 is an example of aThermogravimetric Analysis (TGA) plot outlining the above explanationand the measure of water, light organics and heavy organics.

As noted above, treatment can remove or neutralize heavy metals,transition metals, sodium and phytotoxic organics, polycyclic aromatichydrocarbons, volatile organic compounds (VOCs), other phytotoxins, andeven dioxins. Thus, by treating the biochar in accordance with thetreatment processes set forth and described above, the resulting treatedbiochar has essentially all, and more preferably all, of their poresurfaces modified by the removal, neutralization or both, of one or moredeleterious, harmful, or potentially harmful material that is present inthe starting biochar material.

Dioxins may also be removed through the treatment processes of thepresent invention. Dioxins are released from combustion processes andthus are often found in raw biochar. Dioxins include polychlorinateddibenzo-p-dioxins (PCDDs) (i.e., 75 congeners (10 are specificallytoxic)); polychlorinated dibenzofurans (PCDFs) (i.e., 135 congeners (7are specifically toxic)) and polychlorinated biphenyls (PCBs)(Considered dioxin-like compounds (DLCs)).

Since some dioxins may be carcinogenic even at low levels of exposureover extended periods of time, the FDA views dioxins as a contaminantand has no tolerances or administrative levels in place for dioxins inanimal feed. Dioxins in animal feed can cause health problems in theanimals themselves. Additionally, the dioxins may accumulate in the fatof food-producing animals and thus consumption of animal derived foods(e.g. meat, eggs, milk) could be a major route of human exposure todioxins. Thus, if biochar is used in animal applications, where theanimals ingest the biochar, the ability to remove dioxins from the rawbiochar prior to use is of particular significance.

Results have proven the removal of dioxins from raw biochar by applyingthe treatment process of the present invention. To demonstrate theremoval of dioxins, samples of both raw biochar and biochar, treatedwithin the parameters set forth above, were sent out for testing. Theresults revealed that the dioxins in the raw biochar were removedthrough treatment as the dioxins detected in the raw biochar sample werenot detected in the treated biochar sample. Below is a chart comparingthe test results of measured dioxins in the raw verses the treatedbiochar.

Amount Detected in Raw Amount Detected in Treated Dioxins Biochar SampleBiochar Sample Tetradioxins 26.4 ng/Kg-dry Not detectable Pentadioxins5.86 ng/Kg-dry Not detectable Hexadioxins 8.41 ng/Kg-dry Not detectable

A number of different dioxins exist, several of which are known to betoxic or undesirable for human consumption. Despite the test resultsabove, it is possible that any number of dioxins could be present in rawbiochar depending on the biomass or where the biomass is grown. It isshown, however, in the above testing, that the treatment process of thepresent invention can be used to eliminate dioxins present in rawbiochar.

Seventeen tetra-octo dioxins and furan congeners are the basis forregulatory compliance. Other dioxins are much less toxic. Dioxins aregenerally regulated on toxic equivalents (TEQ) and are represented bythe sum of values weighted by Toxic Equivalency

TEQ=Σ[C_(i)]×TEF_(i)

Factor (TEF)

2,3,7,8-TCDD has a TEF of 1 (most toxic). TEQ is measured as ng/kgWHO-PCDD/F-TEQ//kg NDs are also evaluated. Two testing methods aregenerally used to determine TEQ values: EPA Method 8290 (for researchand understanding at low levels (ppt-ppq); and EPA Method 1613B (forregulatory compliance). Both are based on high resolution gaschromatography (HRGC)/high resolution mass spectrometry (HRMS).

The required EU Feed Value is equal to or less than 0.75 ng/kgWHO-PCDD/F-TEQ//kg. Treated biochar, in accordance with the presentinvention, has shown to have TEQ dioxins less than 0.5 ng/kgWHO-PCDD/F-TEQ//kg, well below the requirement for EU Feed limits of0.75 ng/kg WHO-PCDD/F-TEQ//kg. As further set forth above, treatment canreduce the amount of detectable dioxins from raw biochar such that thedioxins are not detectible in treated biochar. Two methods are used: EPAMethod 8290 (for research and understanding at low levels (ppt-ppq); andEPA Method 1613B (for regulatory compliance). Both are based on highresolution gas chromatography (HRGC)/high resolution mass spectrometry(HRMS).

4. Pore Volume

Generally, a treated biochar sample has greater than 50% by volume ofits porosity in macropores (pores greater than 300 nanometers). Further,results indicate that greater than 75% of pores in treated biochar arebelow 50,000 nanometers. Also, results indicate that greater than 50% byvolume of treated biochar porosity are pores in the range of 500nanometers and 100,000 nanometers. Bacterial sizes are typically 500nanometers to several thousand nanometers. Bacteria and other microbeshave been observed to fit and colonize in the pores of treated biochar,thus supporting the pore size test results.

Macropore volume is determined by mercury porosimetry, which measuresthe meso and/or macro porosity by applying pressure to a sample immersedin mercury at a pressure calibrated for the minimum pore diameter to bemeasured (for macroporosity this is 300 nanometers). This method can beused to measure pores in the range of 3 nm to 360,000 nm. Total volumeof pores per volumetric unit of substance is measured using gasexpansion method.

Depending upon the biomass from which the biochar is derived, mercuryporosimetry testing has shown that washing under differential pressure,using the processes described above, can increase the number of both thesmallest and larger pores in certain biochar (e.g., pine) and canincrease the number of usable smaller pores. Treatment of biochar usingeither vacuum or surfactant does alter the percentage of total usablepores between 500 to 100,000 nanometers and further has varying impacton pores less than 50,000 nanometers and less than 10,000 nanometers.

FIG. 14 is a chart 1400 showing the impact of treatment on pores sizesof biochar derived from coconut. The majority of the coconut basedbiochar pores are less than 10 microns. Many are less than 1 micron.Vacuum processing of the biochar results in small reduction of 10 to 50micron pores, with increase of smaller pores on vacuum processing. Themercury porosimetry results of the raw biochar are represented by 1402(first column in the group of three). The vacuum treated biochar isrepresented by 1404 (second column in the group of three) and thesurfactant treated biochar is 1406 (third column in the group of three).

FIG. 15 is a chart 1500 showing the impact of treatment on pores sizesof biochar derived from pine. The majority of the pine based biocharpores are 1 to 50 microns, which is a good range for micro-biologicals.Vacuum processing results in significant reduction of the 10 to 50micron pores, with an increase of smallest and largest pores. Themercury porosimetry results of the raw biochar are represented by 1502(first column in the group of three). The vacuum treated biochar isrepresented by 1504 (second column in the group of three) and thesurfactant treated biochar is 3006 (third column in the group of three).

5. Electrical Conductivity

The electrical conductivity (EC) of a solid material-water mixtureindicates the amount of salts present in the solid material. Salts areessential for plant growth. The EC measurement detects the amount ofcations or anions in solution; the greater the amount of ions, thegreater the EC. The ions generally associated with salinity are Ca²⁺,Mg²⁺, K⁺, Na⁺, H⁺, NO₃ ⁻, SO₄ ²⁻, Cl−, HCO₃ ⁻, OH⁻. Electricalconductivity testing of biochar was done following the method outlinedin the USDA's Soil Quality Test Kit Guide and using a conventional ECmeter. The biochar sample is mixed with DI water in a 1:1 biochar towater ratio on a volume basis. After thorough mixing, the EC (dS/m) ismeasured while the biochar particles are still suspended in solution.Treatment, as outlined in this disclosure can be used to adjust the ionsin the char. Testing of treated biochar shows its EC is generallygreater than 0.2 dS/m and sometimes greater than 0.5 dS/m.

6. Cation Exchange Capacity

One method for cation exchange capacity (“CEC”) determination is the useof ammonium acetate buffered at pH 7.0 (see Schollenberger, C. J. andDreibelbis, E R. 1930, Analytical methods in base-exchangeinvestigations on soils, Soil Science, 30, 161-173). The material issaturated with 1M ammonium acetate, (NH₄OAc), followed by the release ofthe NH₄ ⁺ ions and its measurement in meq/100 g (milliequivalents ofcharge per 100 g of dry soil) or cmolc/kg (centimoles of charge perkilogram of dry soil). Instead of ammonium acetate another method usesbarium chloride according to Mehlich, 1938, Use of triethanolamineacetate-barium hydroxide buffer for the determination of some baseexchange properties and lime requirement of soil, Soil Sci. Soc. Am.Proc. 29:374-378. 0.1 M BaCl₂ is used to saturate the exchange sitesfollowed by replacement with either MgSO₄ or MgCl₂.

Indirect methods for CEC calculation involves the estimation ofextracted Ca₂ ⁺, Mg₂ ⁺, K⁺, and Na⁺ in a standard soil test usingMehlich 3 and accounting for the exchangeable acidity (sum of H⁺, Al₃ ⁺,Mn₂ ⁺, and Fe₂ ⁺) if the pH is below 6.0 (see Mehlich, A. 1984,Mehlich-3 soil test extractant: a modification of Mehlich-2 extractant,Commun. Soil Sci. Plant Anal. 15(12): 1409-1416). When treated using theabove methods, including but not limited by washing under a vacuum,treated biochars generally have a CEC greater than 5 millieq/l and someeven have a CEC greater than 25 (millieq/l). To some extent, treatmentcan be used to adjust the CEC of a char.

7. Anion Exchange Capacity

Similar to CEC measurements, anion exchange capacity (“AEC”) may becalculated directly or indirectly-saturated paste extraction ofexchangeable anions, Cl⁻, NO₃ ⁻, SO₄ ²⁻, and PO4³⁻ to calculate anionsum or the use of potassium bromide to saturate anions sites atdifferent pHs and repeated washings with calcium chloride and finalmeasurement of bromide (see Rhoades, J. D. 1982, Soluble salts, p.167-179. In: A. L. Page et al. (ed.) Methods of soil analysis: Part 2:Chemical and microbiological properties; and Michael Lawrinenkoa andDavid A. Laird, 2015, Anion exchange capacity of biochar, Green Chem.,2015, 17, 4628-4636). When treated using the above methods, includingbut not limited by washing under a vacuum, treated biochars generallyhave an AEC greater than 5 millieq/l and some even have an AEC greaterthan 20 (millieq/l). To some extent, treatment can be used to adjust theCEC of a char.

8. Hydrophilicity/Hydrophobicity

The ability to control the hydrophilicity of the pores provides theability to load the biochar particles with larger volumes of inoculant.The more hydrophilic the more the biochars can accept inoculant orinfiltrate. Tests show that biochar treated in accordance with the aboveprocesses, using either vacuum or surfactant treatment processesincrease the hydrophilicity of raw biochar. Two tests may be used totest the hydrophobicity/hydrophilicity of biochar: (i) the Molarity ofEthanol Drop (“MED”) Test; and (ii) the Infiltrometer Test.

The MED test was originally developed by Doerr in 1998 and latermodified by other researchers for various materials. The MED test is atimed penetration test that is noted to work well with biochar soilmixtures. For 100% biochar, penetration time of different mixtures ofethanol/water are noted to work better. Ethanol/Water mixtures versessurface tension dynes were correlated to determine whether treatedbiochar has increased hydrophilicity over raw biochar. Seven mixtures ofethanol and deionized water were used with a sorption time of 3 secondson the biochar.

Seven solutions of deionized (“DI”) water with the following respectivepercentages of ethanol: 3, 5, 11, 13, 18, 24 and 36, were made fortesting. The test starts with a mixture having no DI. If the solution issoaked into the biochar in 3 seconds for the respective solution, itreceives the corresponding Hydrophobicity Index value below.

Ethanol % Hydrophobicity Index 0: DI Water 0 Very Hydrophillic  3% 1  5%2 11% 3 13% 4 18% 5 24% 6 36% 7 Strongly Hydrophobic

To start the test the biochar (“material/substrate”) is placed inconvenient open container prepared for testing. Typically, materials tobe tested are dried 110° C. overnight and cooled to room temperature.The test starts with a deionized water solution having no ethanol.Multiple drips of the solution are then laid onto the substrate surfacefrom low height. If drops soak in less than 3 seconds, test recordssubstrate as “0”. If drops take longer than 3 seconds or don't soak in,go to test solution 1. Then, using test solution 1, multiple drops fromdropper are laid onto the surface from low height. If drops soak intothe substrate in less than 3 seconds, test records material as “1”. Ifdrops take longer than 3 seconds, or don't soak in, go to test solution2. Then, using test solution 2, multiple drops from dropper laid ontothe surface from low height. If drops soak into the substrate in lessthan 3 seconds, test records material as “2”. If drops take longer than3 seconds, or don't soak in, go to test solution 3. Then, using testsolution 3, multiple drops from dropper laid onto the surface from lowheight. If drops soak into the substrate in less than 3 seconds, testrecords material as “3”. If drops take longer than 3 seconds, or don'tsoak in, go to solution 4.

The process above is repeated, testing progressively higher numbered MEDsolutions until the tester finds the solution that soaks into thesubstrate in 3 seconds or less. The substrate is recorded as having thathydrophobicity index number that correlates to the solution numberassigned to it (as set forth in the chart above).

Example test results using the MED test method is illustrated below.

MATERIAL HYDROPHOBICITY INDEX Raw Biochars 3 to 5 Treated Biochars 1 to3

Another way to measure and confirm that treatment decreaseshydrophobicity and increases hydrophilicity is by using a mini diskinfiltrometer. For this test procedure, the bubble chamber of theinfiltrometer is filled three quarters full with tap water for bothwater and ethanol sorptivity tests. Deionized or distilled water is notused. Once the upper chamber is full, the infiltrometer is inverted andthe water reservoir on the reserve is filled with 80 mL. Theinfiltrometer is carefully set on the position of the end of themariotte tube with respect to the porous disk to ensure a zero suctionoffset while the tube bubbles. If this dimension is changedaccidentally, the end of the mariotte tube should be reset to 6 mm fromthe end of the plastic water reservoir tube. The bottom elastomer isthen replaced, making sure the porous disk is firmly in place. If theinfiltrometer is held vertically using a stand and clamp, no watershould leak out.

The suction rate of 1 cm is set for all samples. If the surface of thesample is not smooth, a thin layer of fine biochar can be applied to thearea directly underneath the infiltrometer stainless steel disk. Thisensures good contact between the samples and the infiltrometer. Readingsare then taken at 1 min intervals for both water and ethanol sorptivitytest. To be accurate, 20 mL water or 95% ethanol needs to be infiltratedinto the samples. Record time and water/ethanol volumes at the times arerecorded.

The data is then processed to determine the results. The data isprocessed by the input of the volume levels and time to thecorresponding volume column. The following equation is used to calculatethe hydrophobicity index of R

$I = {{at} + {b\sqrt{t}}}$ a:  Infiltration  Rate, cm/sb:  Sorptivity, cm/s^(1/2)$R = {1.95*\frac{b_{ethanol}}{b_{water}}}$

FIG. 16 illustrates one example of the results of a hydrophobicity testperformed on raw biochar, vacuum treated biochar and surfactant treatedbiochar. As illustrated, both the vacuum treated and surfactant treatedbiochar are more hydrophilic than the raw biochar based upon the lowerIndex rating. In accordance with the test data in FIG. 16, thehydrophobicity of raw biochar was reduced 23% by vacuum processing and46% by surfactant addition.

As an example, raw biochar and treated biochar were tested with ethanoland water, five times for each. The results below show that thehydrophobicity index of the treated biochar is lower than the rawbiochar. Thus, tests demonstrate that treating the biochar, using themethods set forth above, make the biochar less hydrophobic and morehydrophilic.

MATERIAL HYDROPHOBICITY INDEX Dried Raw Biochar 12.9 Dried VacuumTreated Biochar 10.4 Dried Surfactant Treated Biochar 7.0 As Is RawBiochar 5.8 As Is Vacuum Treated Biochar 2.9

Further, through the treatment processes of the present invention, thebiochar can also be infused with soil enhancing agents. By infusingliquid into the pore structure through the application of positive ornegative pressure and/or a surfactant, alone or in combination, providesthe ability to impregnate the macropores of the biochar with soilenhancing solutions and solids. The soil enhancing agent may include,but not be limited to, any of the following: water, water solutions ofsalts, inorganic and organic liquids of different polarities, liquidorganic compounds or combinations of organic compounds and solvents,mineral and organic oils, slurries and suspensions, supercriticalliquids, fertilizers, plant growth promoting rhizobacteria, free-livingand nodule-forming nitrogen fixing bacteria, organic decomposers,nitrifying bacteria, phosphate solubilizing bacteria, biocontrol agents,bioremediation agents, saprotrophic fungi, ectomycorrhizae andendomycorrhizae, among others.

9. Impregnation and/or Inoculation with Infiltrates or Additives

In addition to mitigating or removing deleterious pore surfaceproperties, by treating the pores of the biochar through a forced,assisted, accelerate or rapid infiltration process, such as thosedescribed above, the pore surface properties of the biochar can beenhanced. Such treatment processes may also permit subsequentprocessing, may modify the pore surface to provide predeterminedproperties to the biochar, and/or provide combinations and variations ofthese effects. For example, it may be desirable or otherwiseadvantageous to coat substantially all, or all of the biochar macroporeand mesopore surfaces with a surface modifying agent or treatment toprovide a predetermined feature to the biochar, e.g., surface charge andcharge density, surface species and distribution, targeted nutrientaddition, magnetic modifications, root growth facilitator, and waterabsorptivity and water retention properties.

By infusing liquids into the pores of biochar, it has been discoveredthat additives infused within the pores of the biochar provide a timerelease effect or steady flow of some beneficial substances to theenvironment, e.g. root zones of the plants, and also can improve andprovide a more beneficial environment for microbes which may reside ortake up residence within the pores of the biochar. In particular,additive infused biochars placed in the soil prior to or after plantingcan dramatically reduce the need for high frequency application ofadditives, minimize losses caused by leaching and runoff and/or reduceor eliminate the need for controlled release fertilizers. They can alsobe exceptionally beneficial in animal feed applications by providing aneffective delivery mechanism for beneficial nutrients, pharmaceuticals,enzymes, microbes, or other substances.

For purposes of this application, “infusion” of a liquid or liquidsolution into the pores of the biochar means the introduction of theliquid or liquid solution into the pores of the biochar by a means otherthan solely contacting the liquid or solution with the biochar, e.g.,submersion. The infusion process, as described in this application inconnection with the present invention, includes a mechanical, chemicalor physical process that facilitates or assist with the penetration ofliquid or solution into the pores of the biochar, which process mayinclude, but not be limited to, positive and negative pressure changes,such as vacuum infusion, surfactant infusion, or infusion by movement ofthe liquid and/or biochar (e.g., centrifugal force and/or ultrasonicwaves) or other method that facilitates, assists, forces or acceleratesthe liquid or solution into the pores of the biochar.

Prior to infusing the biochar, the biochar, as described in detailabove, may be washed and/or moisture adjusted. FIG. 17 is a flow diagram1700 of one example of a method for infusing biochar with an additive.Optionally, the biochar may first be washed or treated at step 1702, thewash may adjust the pH of the biochar, as described in more detailabove, or may be used to remove elemental ash and other harmful organicsthat may be unsuitable for the desired infused additive. Optionally, themoisture content of the biochar may then be adjusted by drying thebiochar at step 1704, also as described in further detail above, priorto infusion of the additive or inoculant at step 1706.

In summary, the infusion process may be performed with or without anywashing, prior pH adjustment or moisture content adjustment. Optionally,the infusion process may be performed with the wash and/or the moistureadjustment step. All the processes may be completed alone or in theconjunction with one or more of the others.

Through the above process of infusing the additive into the pores of thebiochar, the pores of the biochar may be filled by 25%, up to 100%, withan additive solution, as compared to 1-20% when the biochar is onlysubmerged in the solution or washed with the solution for a period ofless than twelve hours. Higher percentages may be achieved by washingand/or drying the pores of the biochar prior to infusion.

Data have been gathered from research conducted comparing the results ofsoaking or immersion of biochar in liquid versus vacuum impregnation ofliquid into biochar. These data support the conclusion that vacuumimpregnation provides greater benefits than simple soaking and resultsin a higher percentage volume of moisture on the surface, interstitiallyand in the pores of the biochar.

In one experiment, equal quantities of pine biochar were mixed withequal quantities of water, the first in a beaker, the second in a vacuumflask. The mixture in the beaker was continuously stirred for up to 24hours, then samples of the suspended solid were taken, drained andanalyzed for moisture content. The mixture in the vacuum flask wasconnected to a vacuum pump and negative pressure of 15″ was applied.Samples of the treated solid were taken, drained and analyzed formoisture content. FIG. 18 is a chart illustrating the results of theexperiment. The lower graph 1802 of the chart, which shows the resultsof soaking over time, shows a Wt. % of water of approximately 52%. Theupper graph 1804 of the chart, which shows the results of vacuumimpregnation over time, shows a Wt. % of water of approximately 72%.

FIGS. 19a and 19b show two charts that further illustrate that the totalwater and/or any other liquid content in processed biochar can besignificantly increased using vacuum impregnation instead of soaking.FIG. 19a compares the mL of total water or other liquid by retained by 1mL of treated biochar. The graph 1902 shows that approximately 0.17 mLof water or other liquid are retained through soaking, while the graph1904 shows that approximately 0.42 mL of water or other liquid areretained as a result of vacuum impregnation. FIG. 19b shows that theretained water of a biochar subjected to soaking consists entirely ofsurface and interstitial water 1906, while the retained water of abiochar subjected to vacuum impregnation consists not only of surfaceand interstitial water 1908 a, but also water impregnated in the poresof the biochar 1908 b.

In addition, as illustrated by FIG. 20, the amount of moisture contentimpregnated into the pores of vacuum processed biochars by varying theapplied (negative) pressure during the treatment process. The graphs offour different biochars all show how the liquid content of the pours ofeach of them increase to 100% as the vacuum is increased.

The pores may be substantially filled or completely filled withadditives to provide enhanced performance features to the biochar, suchas increased plant growth, nutrient delivery, water retention, nutrientretention, disadvantageous species control, e.g., weeds, disease causingbacteria, insects, volunteer crops, etc. By infusing liquid deep intothe pore structure through the application of positive or negativepressure, surfactant and/or ultrasonic waves, alone or in combination,provides the ability to impregnate the mesopores and macropores of thebiochar with additives, that include, but are not limited to, soilenhancing solutions and solids. It should be noted that using theseinfusion techniques allows for impregnating the pores with additivesthat are more fragile. For example, since heating is not a requirementfor these infusion techniques, microbes, chemicals, or compounds can beinfused without risk of destroying the microbes or changing chemicals orcompounds due to high temperatures. Also the process can be done at lowtemperatures to infuse chemicals that have low boiling points to keepthem a liquid.

The additive may be a soil enhancing agent that includes, but is not belimited to, any of the following: water, water solutions of salts,inorganic and organic liquids of different polarities, liquid organiccompounds or combinations of organic compounds and solvents, mineral andorganic oils, slurries and suspensions, supercritical liquids,fertilizers, PGPB (including plant growth promoting rhizobacteria,free-living and nodule-forming nitrogen fixing bacteria, organicdecomposers, nitrifying bacteria, and phosphate solubilizing bacteria),enzymes, biocontrol agents, bioremediation agents, saprotrophic fungi,ectomycorrhizae and endomycorrhizae, among others.

Fertilizers that may be infused into the biochar include, but are notlimited to, the following sources of nitrogen, phosphorous, andpotassium: urea, ammonium nitrate, calcium nitrate, sulfur, ammoniumsulfate, monoammonium phosphate, ammonium polyphosphate, potassiumsulfate, or potassium chloride.

Similar beneficial results are expected from other additives, such as:bio pesticides; herbicides; insecticides; nematicides; plant hormones;plant pheromones; organic or inorganic fungicides; algicides;antifouling agents; antimicrobials; attractants; biocides, disinfectantsand sanitizers; miticides; microbial pesticides; molluscicides;bacteriacides; fumigants; ovicides; repellents; rodenticides,defoliants, desiccants; insect growth regulators; plant growthregulators; beneficial microbes; and, microbial nutrients or secondarysignal activators, that may also be added to the biochar in a similarmanner as a fertilizer. Additionally, beneficial macro- andmicro-nutrients such as, calcium, magnesium, sulfur, boron, zinc, iron,manganese, molybdenum, copper and chloride may also be infused into thebiochar in the form of a water solution or other solvent solution.

Examples of compounds, in addition to fertilizer, that may be infusedinto the pores of the biochar include, but are not limited to:phytohormones, such as, abscisic acid (ABA), auxins, cytokinins,gibberellins, brassinosteroies, salicylic acid, jasmonates, planetpeptide hormones, polyamines, karrikins, strigolactones;2,1,3-Benzothiadiazole (BTH), an inducer of systemic acquired resistancethat confers broad spectrum disease resistance (including soil bornepathogens); signaling agents similar to BTH in mechanism or structurethat protects against a broad range or specific plant pathogens; EPSPSinhibitors; synthetic auxins; photosystem I inhibitors photosystem IIinhibitors; and HPPD inhibitors.

In one example, a 1000 ppm NO₃ ⁻ N fertilizer solution is infused intothe pores of the biochar. As discussed above, the method to infusebiochar with the fertilizer solution may be accomplished generally byplacing the biochar in a vacuum infiltration tank or other sealablemixing vessel, chamber or tank. When using vacuum infiltration, a vacuummay be applied to the biochar and then the solution may be introducedinto the tank. Alternatively, the solution and biochar may both beintroduced into the tank and, once introduced, a vacuum is applied.Based upon the determined total pore volume of the biochar or theincipient wetness, the amount of solution to introduce into the tanknecessary to fill the pore of the biochar can be determined. Wheninfused in this manner, significantly more nutrients can be held in agiven quantity of biochar versus direct contact of the biochar with thenutrients alone.

When using a surfactant, the biochar and additive solution may be addedto a tank along with 0.01-20% of surfactant, but more preferably 1-5% ofsurfactant by volume of fertilizer solution. The surfactant or detergentaids in the penetration of the wash solution into the pores of thebiochar. The same or similar equipment used in the vacuum infiltrationprocess can be used in the surfactant treatment process. Although it isnot necessary to apply a vacuum in the surfactant treatment process, thevacuum infiltration tank or any other mixing vessel, chamber or tank canbe used. Again, while it is not necessary to apply a vacuum, a vacuummay be applied or the pressure in the vessel may be changed. Further,the surfactant can be added with or without heat or cooling either ofthe infiltrate, the biochar, the vessel itself, or any combination ofthe three.

The utility of infusing the biochar with an additive is that the poresin biochar create a protective “medium” for carrying said additive tothe environment. As an example when the additive is a fertilizer thenutrient infused biochar provides a more constant supply of availablenutrients to the soil and plants and continues to act beneficially,potentially sorbing more nutrients or nutrients in solution even afterintroduction to the soil. By infusing the nutrients in the pores of thebiochar, immediate oversaturation of the soil with the nutrients isprevented and a time released effect is provided. This effect isillustrated in connection with FIGS. 18 and 19 below. As demonstrated inconnection with FIGS. 18 & 19 below, biochars having pores infused withadditives, using the infusion methods described above, have been shownto increase nutrient retention, increase crop yields and provide asteadier flow of fertilizer to the root zones of the plants.

FIG. 21 is a chart showing improved mass yield in lettuce withfertilizer infused biochar using vacuum impregnation. FIG. 21 comparesthe mass yield results of lettuce grown in different environments. Oneset of data measurements represents lettuce grown in soil over a certainset time period with certain, predetermined amounts of fertilizerinfused into the biochar. A second set of data represents lettuce grownin soil over a certain set period of time with the same amount ofunimpregnated biochar added at the beginning of the trial and certainpredetermined amounts of NPK solution added to the soil over time.Growth comparisons were made between the same amount of fertilizersolution infused into the biochar as added directly to the soil, usingthe same watering schedule. As illustrated, the test resultsdemonstrated a 15% yield increase in growth when infusing approximately750 mg/pot of NPK into the biochar than when applying it directly to thesoil. Similarly, the same mass yield of lettuce is achieved at 400 mgNPK/pot with infused biochar than at 750 mg/pot when adding thefertilizer solution directly to the soil.

FIG. 22 is a chart illustrating the concentration of nitrate (N) foundin distilled water after washing differentially treated biochar. In theillustrated example, two biochar samples (500 ml each) mixed with 1000ppm NO₃ ⁻ N fertilizer solution were washed with distilled water. Theresulting wash was then tested for the presence of nitrate (N), measuredin ppm. In one sample, the biochar was submerged in and mixed with thenutrient solution. In the other example, the biochar was mixed or washedwith a nutrient solution augmented with 1% surfactant by volume (i.e., 1ml of surfactant per 100 ml of fertilizer solution) in a tumbler. Inboth examples, the biochar was not dried completely before infusion withthe NO₃ ⁻ N fertilizer solution, but used as received with a moisturecontent of approximately 10-15%. In both examples, the biochar was mixedwith solution and/or surfactant (in the case of a second sample) with abench scale tumbler, rotating the drum for four (4) minutes withoutvacuum. The results demonstrate that the biochar treated with the 1%surfactant increases the efficiency of infiltrating nitrate fertilizerinto biochar and then demonstrates the release of the nutrient overtime. To yield the above data, the test was repeated six times for eachtreatment sample, with 10 washes for each sample per repeat test.

The above are only a few examples of how additive infused biochar may beproduced for different uses. Those skilled in the art will recognizethat there may be other mechanisms for infusing fertilizer or other soiladditives into the pores of the biochar without departing from the scopeof the invention. Those skilled in the art will further recognize thatthe present invention can be used on any type of soil application,including, but not limited to, the following: crops, turf grasses,potted plants, flowering plants, annuals, perennials, evergreens andseedlings, as will be further described below.

For example, in another implementation, additive infused biochar may beproduced for use for consumption by animals and/or humans. Biochar maybe infused in the same manner as described above with nutrients (such ascarbohydrates, minerals, proteins, lipids), vitamins, drugs and/or othersupplements (such as enzymes or hormones, to name a few), or acombination of any of the foregoing, for consumption by either humansand/or animals. Coloring, flavor agents and/or coating may also beinfused into the pores of the biochar or applied to the surface. Theforegoing may be included to enhance the performance of the substance inthe digestive tract or to ease or facilitate the ingestion of thebiochar.

D. Biochar as a Habitat for Microorganisms

Biotechnology, specifically the use of biological organisms, usuallymicroorganisms, to address chemical, industrial, medical, oragricultural problems is a growing field with new applications beingdiscovered daily. To date, much research has focused on identifying,developing, producing and deploying microbes for various uses. However,despite much work on the microbes themselves, relatively little work hasbeen performed on how to carry, deliver, and encourage the successfulestablishment of these microbes in their targeted environment. Mostcurrent technology for microbial carriers in agriculture is based ontechnologies or products that are highly variable and, in many cases,lead to highly unpredictable performance of microbes in the field. Forexample, many commercial microbes in agricultural settings are deliveredon peat, clay, or other carriers derived from natural sources,accompanied by limited engineering or process control.

Biochar have a proclivity to interact positively with many microbesrelevant to plant health, animal health, and human public healthapplications. In fact, there has been a level of initial researchfocused on inoculating biochar with microbes and/or using biochar inconjunction with microbes or materials with microbes, e.g. compost. Seeco-owned U.S. Pat. No. 8,317,891 Method for Enhancing Soil Growth UsingBio-char and Fischer et al., and Synergisms between compost and biocharfor sustainable soil amelioration 2012http://www.intechopen.com/source/pdfs/27163/InTech-Synergisms_between_compost_and_biochar_for_sustainable_soil_amelioration.pdf.

However, biochars, especially in raw form, often suffer from manycharacteristics which make their interaction with microbial organismsextremely unpredictable. Key among these undesirable characteristics isa high degree of variability. Because of this and other factors, biocharhas been, to date, unused in large scale commercial biotechnologyapplications. There are several methods by which this variability can beameliorated. At a high level, the methods to overcome these challengesfall into two categories: (i) making the biochar a more favorablehabitat for the microbes—either by modifying its properties, addingmaterials beneficial to microbes, or removing materials deleterious tomicrobes, or (ii) inoculating, applying, or immobilizing the microbes onthe biochar in ways that mitigate the underlying variability in thematerial. Both of these high-level methods can be used independently orin conjunction and have been shown to have a significant impact on thesuitability of biochar in many biotechnology applications.

Before delving into the varying treatment methods that will turn thebiochar into a microbial carrier or co-deploying with microbes, it isimportant to be able to view biochar as a habitat for microbes. Biochar,especially treated biochar, has many physical properties that make itinteresting as a microbial habitat. The most obvious of these is itsporosity (most biochars have a surface area of over 100 m2/g and totalporosity of 0.10 cm3/cm3 or above). Furthermore, many biochars havesignificant water holding and nutrient retention characteristics whichmay be beneficial to microbes. Previous disclosure has outlined howthese characteristics can be further improved with treatment, e.g., U.S.patent application Ser. No. 15/156,256, filed on May 16, 2016, andtitled Enhanced Biochar.

However, recent data indicates that the Earth may be home to more thanone trillion independent species of microbes (See Kenneth J. Locey andJay T. Lennon, Scaling laws predict global microbial diversity,Proceedings of the National Academy of Science, vol. 113 no. 21 (seefull text at http://www/pnas.org/content/113/21/5970.full). Clearly,each of these microbial species does not require an identical habitat.In fact, many have evolved in different conditions and thrive indifferent environments. Biochar, due to its organic origins, porosity,and amenability to treatment seems to be an extremely desirable baseproduct to be used in the construction of microbial carriers orco-deployment of microbes. If the properties of the biochar can be madeto match the properties expected by particular microbes, or groups ofmicrobes, empirical data has shown that a much greater impact can bedelivered in many applications—whether the targeted biochar is used as acarrier, substrate, co-deployed product, or merely is introduced intothe same environment at a separate time. It stands to reason, as manyreal-world environments are composed of very complex microbialecosystems, that giving certain microbes in these ecosystems a morefavorable habitat, can ultimately help those microbes to become moresuccessfully established, and potentially shift the entire ecosystembased on their improved ability to compete for resources. Clearly thisis a very desirable characteristic when the successful deployment andestablishment of a targeted microbe into a new environment is a desiredoutcome.

There are many properties of a habitat which may be important to certainmicrobes, but some of the most important are: pH, hydrophobicity orhydrophilicity, ability to hold moisture, ability to retain and exchangecertain types of nutrients, ion exchange capacity (cationic andanionic), physical protection from predatory or competitive microbes orprotozoa (usable and inhabitable porosity), presence or absence ofnutrients, micronutrients, or sources of metabolic carbon, ability tohost other symbiotic microbes or plant systems (such as plant roottissue), or others which may be important to various types or species ofmicrobes. Ability to either enhance or suppress the availability ofcertain enzymes can also be an extremely important factor in building aviable habitat. This invention focuses on methods and systems that canbe used to consistently produce biochar which has these targetedcharacteristics, methods that can be used to effectively create aparticular formulation of biochar targeted to match a particular microbeor group of microbes, and techniques for deploying the desired microbesalong with this targeted biochar, through inoculation, co-deployment,integrated growth/fermentation, or other methods.

By using treatment properties disclosed previously, proper feedstockselection, and control of the pyrolysis process, the following are some,but not all, of the properties that can be consistently targeted andcontrolled at production scales to improve the biochar for use withmicrobes or as a microbial carrier. Examples of those properties include(1) pH, (2) hydrophobicity, (3) sodium levels, (4) usable pore sizedistribution and usable pore volume. (5) particle size and distribution,(6) exterior and interior surface geometry, (7) nutrient exchange, (8)exterior and interior surface geometry, (9) useable carbon or energysource, (10) toxic materials or compounds, (11) surfacestructure/crystals/tortuosity, (12) compatibility with biofilmformations, and (13) enzyme activity.

1. pH

It is well known that various microbes prefer varying levels of acidityor alkalinity. For example, acidophiles have evolved to inhabitextremely acidic environments. Likewise, alkaliphiles prefer more basic(alkali) environments. It has been clearly shown that the methodsoutlined for treating biochars can product targeted pH values that canbe sustained over long periods of time.

2. Hydrophobicity

There are several common sources of hydrophobicity in porouscarbonaceous materials. One of them is the occurrence of hydrophobicorganic compounds on the surface of the char—typically residual from thepyrolysis process. Targeted removal of these compounds is a method toimprove the hydrophobicity of porous carbonaceous substances. Thesecompounds can be removed in a non-selective way by increasing thepyrolysis temperature of the biomass to a level at which the compoundswill disassociate with the material and become gaseous. This method,while useful, is very broad, and can also remove other desirablecompounds as well as changing the surface chemistry of the residualcarbon, increasing ash percentages, or reducing carbon yield by reactingand removing more carbon than is necessary. These compounds can also beselectively removed by the application of a targeted solvent using themechanisms previously disclosed to infiltrate liquids into the porevolume of the material. This method is also effective, and has shown tobe much more predictable in the removal of certain compounds. Since thevast majority of microbes rely heavily on water for both transport andlife, the easy association of water with a material has a large bearingon its ability to sustain microbial life.

3. Sodium Levels

Differing types of microbes have varying proclivities for the presenceof sodium. Some microbes Halobacterium spp., Salinibacter ruber,Wallemia ichthyophaga prefer high levels of salinity, while othersprefer moderate or limited levels of sodium. Sodium can be removed frombiochar by either simple washing, or more preferably and effectively,treatment methods which infuse a solvent (most commonly water, althoughothers may be used) into the pores of the material. Sodium can be added,by using the same methods except instead of using a solvent, the liquidbeing washed with or infused is a solution high in sodium content.Additionally, since sodium usually manifests itself as a cation insolution, temporary or permanent adjustment of the cationic exchangecapacity (CEC) of the material through treatment which impacts theability of the material to exchange cations. Lowering the CEC of thematerial will in many cases reduce its ability to exchange sodiumcations, while raising the CEC will typically enhance the ability of thematerial to exchange sodium cations, with exceptions occurring if othercations are present in quantities that cause them to preferentiallyexchange instead of the sodium cations present. Finally, differingbiomass feedstock contains differing levels of sodium—selecting anappropriate feedstock prior to pyrolysis will result in a raw oruntreated biochar with reasonably controlled levels of sodium. Forexample, pine wood, when pyrolyzed, results in a raw char with lowerlevels of sodium, while coconut shells result in char with higher levelsof sodium after pyrolysis.

Untreated Untreated Untreated ASH Coconut Pine Pine Composition ShellBiochar Biochar #1 Biochar #2 Ultimate Analysis - Moisture free resultsAsh 6.7% 9.2% 3.6% Ash Composition Sodium Oxide, as 5.7% 1.2% 0.8% Na2ORegardless, it should be clear that there are various methods availableto produce final product with a targeted sodium level, making itsuitable for various microbes depending on their preference for anenvironment with a certain sodium level.

4. Usable Pore Size Distribution and Usable Pore Volume

One very important quality of a microbial habitat is the availability ofshelter from environmental or biological hazards. A few examples ofenvironmental hazards are high temperature, UV radiation, or lowmoisture, while an example of a biological hazard is the existing ofpredatory multicellular microbes such as protozoa, including bothflagellates and ciliates. In order for a particle or material to provideshelter for microbes, at least two conditions must be present: (i) Thematerial must consist of pores or openings of a size which can beinhabited by the microbe in question (ii) but prevent the hazard fromentering (e.g. pore size smaller than the size of predators, such asprotozoa, or deep enough to be shaded from UV rays) and, (iii) the poresmentioned previously must be usable—namely, they should not be occupiedby solid matter (clogged) and/or they should not contain substances thatare toxic or undesirable for the microbe in question. In some cases, thepore size distribution of a biochar can be adjusted by the selection ofthe biomass feedstock to be pyrolyzed and the conditions of thepyrolysis process itself. For example, pine wood has a relatively narrowpore size distribution, with most pores falling in the range from 10-70μm. Coconut shells, on the other hand, have a much wider sizedistribution, with many pores below 1 μm, and also a high percentage ofporosity above 100 μm. It is theorized that materials with pores of asingle size or where most pores are of similar size can potentially begood carriers or habitats for certain, targeted microbes, whilematerials consisting of broader ranges of pore sizes may be betterhabitats for communities, consortia or groups of microbes, where eachmicrobe may prefer a slightly different pore size. Furthermore, the poresize of a material may also be controlled during the pyrolysis processby increasing temperature or performing “activation” or other stepscommon in activated carbon production to react or remove carbon, leavinglarger pores, or exposing availability of pores that were onceinaccessible from the exterior surface of the material. Adjusting theparticle size of the material may also change the pore size distributionin at least two ways: (i) exposing pores that were not available oraccessible previously, or (ii) destroying larger pores by fracturing,splitting, or dividing them. In many cases, raw biochar may contain aproper pore size distribution, but for one reason or another, the poresare not usable by the microbes in question. In other cases, the poresize distribution provided by the natural feedstock may be undesirable.Both properties may also be impacted through treatment of the rawbiochar itself. Larger pores can be created using strong acids or othercaustic substances either by simple washing or through forced or rapidinfusion into the pores. Conversely, a material with fewer usable poresmay be created by intentionally “clogging” or filling the larger poreswith either solids, gums, or liquids designed to stay resident in thepores themselves. This treatment may be done in a controlled way to onlypartially fill the pores. For example, one could infuse a limited amountof heated liquid, such as a resin, that will become solid at normalatmospheric temperatures. If the volume of liquid used is less than theavailable pore volume of the material being infused, some of theporosity of the material will be left untreated and available for use.Most importantly, and most commonly, usable pore volume may be increasedthrough the act of simply removing contaminants (physical or chemical)from the pores. Rapid infusion and extraction of liquids may be used toaccomplish this. As discussed previously, appropriate solvents may beinfused or extracted to remove chemical contaminants. Additionally,gasses or liquids may be driven into or out of the pores to force theremoval of many solid obstructions, such as smaller particles of ash orsimply smaller particles of raw biochar which may have become lodged inthe pore in question. Regardless of the mechanism used, it has beenshown that the available, uncontaminated, usable pore volume and poresize has a major role in determining the efficacy of biochars inmicrobial roles.

FIGS. 23 and 24 are images that show how different sized bacteria willfit in different biochar pore size structures. FIG. 23 is rod-shapedgram-positive bacteria, Bacillus thuringiensis israelensis, in a treatedpine biochar, with pore openings of ˜10-20 μm and bacteria of ˜2-5 μm.FIG. 24 is rod-shaped gram-negative bacteria, Serratia liquefaciens, ina treated coconut shell biochar, with pore openings of ˜2-10 μm andbacteria of ˜1-2 μm.

In addition, total pore volume in the size of 5-50 μm has been shown tocorrelate with microbial release rate after inoculation on treatedbiochar. FIG. 25 illustrates release rate data verse total pore volumedata for both coconut shell and pine based treated biochars inoculatedwith a releasable bacteria. As illustrated in FIG. 25, the data wasplotted in a graph, and clearly shows that as pore volume increases sodoes the release rate.

5. Exterior and Interior Surface Geometry

Two important properties of microbial carriers are: (i) their ability torelease microbes from their surfaces and (ii) their ability toimmobilize or stabilize microbes on their surfaces. Depending on thefinal application or use of the carrier, one or both of these propertiesmay be desired. For example, for carriers designed to quickly release amicrobe into a targeted domain such as a lake, river, or other waterway,the release characteristics of the material are paramount. For otherapplications, such as applications of certain symbiotic microbes inagriculture, rapid release may be undesirable, rather it may beimportant to sustain the microbes within the porosity of the materialuntil plant tissue, such as root biomass, is nearby to provide nutritionfor the microbes in question. The surface and pore geometry of thematerial used as a carrier can be critical to determine this behavior.For example, material with generally smooth, uniform surfaces willtypically release many microbes much more effectively, while materialwith more rugged, varied, tortuous pore surfaces and geometry willtypically retain and immobilize microbes more effectively. The biomassused in the production of the final material is one of the mostimportant factors in surface geometry. However, even this quality can bealtered through treatment. Specifically, smooth surfaces may be etchedby implementing the treatment and infusion processes previouslydisclosed with strong acids, rendering them rougher. Conversely, roughsurfaces may be treated with either organic or inorganic compounds tocoat and remove contour. Mechanical means may also be used to affectchanges in particle geometry. Many forms of charred material haverelatively low crush strength and are relatively brittle. The methodused to grind, or size particles can have a large impact on the geometryof the final particles. For example, particles milled using a ball millor other type of grinding technology will typically have a smootherexterior geometry after the milling is complete and may lose a goodamount of their porosity through the simple mechanical crushing ofpores. However, particles sized using ultrasonic vibrations or evensimple physical vibrations to shatter, rather than crush largerparticles into smaller ones, will typically retain their geometry, orsometimes result in smaller particles with more rugged geometries thanthe particles at the beginning. It should be apparent to one skilled inthe art that there are various mechanical mechanisms available to effectthese changes, but the resulting particles can be tailored to meet aparticular microbial release or immobilization outcome.

6. Particle Size and Distribution

It is well known that the particle size and particle size distributionof a material has a key impact on its formulation as a microbialcarrier. In many cases, these factors are very different for porouscarbonaceous materials than they are for other common microbialcarriers. In standard carriers, typically the reduction of particle sizeis a method used to increase surface area, and thus the area availableto support, immobilize, and carry microbes. However, in porousmaterials, specifically materials with a large volume of usable interiorporosity, sometimes a reduction in particle size does not cause a largeincrease in the usable surface area—specifically because the interiorsurfaces of the material were already exposed, and reducing the size ofthe particle does not change that fact. This leads to a somewhatcounterintuitive behavior in some cases in which the reduction of theparticle size of a porous material actually degrades its performance asa microbial carrier, due to the phenomena that surfaces that were oncesheltered inside the material are exposed as exterior surfaces when thematerial is split or crushed, making the material less desirable as ahabitat for microbes that require shelter from the surroundingenvironment. Additionally, at times the actual distribution of particlesizes can be a key factor in performance. As a simple example, imaginean aggregated material which consists of only two particle sizes: 1 mmand 1 μm. Furthermore, imagine that 50% of the mass of the aggregateresided in the 1 mm particles with the remainder in the 1 μm particles.Lastly, imagine that the 1 mm particles were porous carbonaceousparticles with an average pore size of approximately 50 μm. It should beclear that if this aggregate was placed in a container and agitated,that a good portion of the 1 μm particles would end up inhabiting thepore volume of the 1 mm particles, impacting their usability. In fact,this is the behavior that we see in practice. Therefore, for certainmicrobial applications, it is desirable to remove extremely smallparticles, often referred to as fines, from the aggregate. This has theadditional benefit of reducing dust during application, which isparticularly important in aerial applications, and reducing the level ofsurface runoff for applications in water, which also is important incertain microbial applications. The small particles may be removedthrough several methods such as sieving, blowing or aerodynamic removal,separation with either stationary or moving liquids (hydrostatic orhydrodynamic separation) of various viscosities, temperatures, flowrates, etc. However, at times, having a mixture of smaller and largerparticles can be desirable. The most common cases are when communitiesof microbes are to be deployed, or the aggregate is to remain generallyintact for a period of time (fermentation applications, long termstorage applications, or preparation for other formulation uses such aspalletization), in which case, the interparticle void space is also animportant factor and can be optimized for a particular microbe or set ofmicrobes by providing a range of particle sizes and geometries.

7. Nutrient Exchange

The ability of a material to hold or exchange nutrients is an incrediblyimportant characteristic, not only for microbial, but also for generalagricultural applications. There are two primary mechanisms that porouscarbonaceous materials can exchange nutrients: (i) sorption or retentionof the nutrients on the interior and exterior surfaces of the material,and (ii) retention of the nutrients either in suspension or solution inliquid or gasses residing in the pore volume of the material. Bothmechanisms are very useful, but also very different in function. Surfacesorption or retention is driven by two main properties, among others:(i) ion exchange capacity of the material and, (ii) reactivity orelectrical charge of compounds present on or coating the surfaces of thematerial. Retention of nutrients in solution or suspension are impactedby other, different characteristics of the material, such ashydrophilicity, oil sorption capacity, usable pore volume and pore sizedistribution, and interior pore geometry and tortuosity. The surfaceretention of nutrients can be targeted by selecting the feedstockbiomass (some materials render a char after pyrolysis with vastlydiffering ionic exchange capacities (CEC and AEC) than others). It canalso be impacted by adjusting pyrolysis conditions. Higher pyrolysistemperatures tend to reduce CEC and nutrient adsorption capability. SeeGai, Xiapu et al. “Effects of Feedstock and Pyrolysis Temperature onBiochar Adsorption of Ammonium and Nitrate.” Ed. Jonathan A. Coles. PLoSONE 9.12 (2014): e113888. PMC. Web. 19 Nov. 2016. In addition, thesurface retention of nutrients can be impacted by treating the surfacesof the material with substances targeted towards adjusting the ionicexchange characteristics. For example, using the previously disclosedtreatment methods to infuse H₂O₂ into the pores of the carbonaceousmaterial and then evaporating the liquid can increase the cationicexchange properties of the material.

Furthermore, another way to exchange nutrients more efficiently is touse the pore volume rather than, or in addition to, the poresurfaces—namely keeping the nutrients in solution or liquid or gaseousform and placing them in the volume of the pores rather than attemptingto sorb them on the surfaces of the material. This can be an incrediblyuseful technique not only for plant life and soil health, but also formicrobes. The food sources can vary from simple to complex such asglucose, molasses, yeast extract, kelp meal, or bacteria media (e.g.MacConkey, Tryptic Soy. Luria-Bertani). When using the pore volume toexchange nutrients in this way, it should be clear that a wide varietyof nutrients may be used, and targeted combinations of pore volume,size, and nutrition can be produced to assist in the delivery,establishment, or successful colonization of targeted microorganisms orgroups of microorganisms. It should be clear by this point that merelyimmersing the biochar or porous carbonaceous material in a liquidnutrient broth may be partially effective in filling the pore volume orcoating the pore surfaces with these nutrients and should be consideredwithin the scope of this invention, however using the treatmenttechniques outlined in this and related disclosures is much moreeffective at both coating the surfaces and infusing nutrition into thepore volume of the material itself. Since many microbes rely on liquidfor mobility, placing liquid into the pore volume of the material is inmany cases a prerequisite for successfully infusing, carrying, ordelivering microbes.

8. Usable Carbon or Energy Sources

Related to the ability to improve nutrient exchange is the ability totreat the pore volume, pore surfaces, exterior surfaces, or anycombination of these with not only custom broths or growth media, butalso other forms of carbon known to be beneficial to microbes and plantlife. Some examples of this are carbohydrates (simple and complex),humic substances, plant macro and micronutrients such as nitrogen (inmany forms, such as ammonium and nitrates), phosphorous, potassium,iron, magnesium, calcium, and sulfur and trace elements such asmanganese, cobalt, zinc, copper, molybdenum. These nutrients may eitherbe infused in liquid or gaseous form, or even as a suspended solid inliquid. The liquid may be left in the pores, or may be removed. Ifremoved through evaporation, nutrients in solution or suspended solidsmay be left behind, while if removed by mechanical or physical means, aportion of the liquid may be left behind as well as some solids. Itshould be noted that the various forms of removal have differingadvantages and disadvantages and that many energy sources may be addedeither at the same time or in sequence, with one, or many, removal stepsin between treatment or infusion steps.

9. Toxic Materials or Compounds

The selective addition or removal of materials or substances known to betoxic to a certain microbe or lifeform is a key step in preparation ofbiochar for use as a microbial habitat or carrier. It has been shown,that through treatment, potentially toxic compounds can be removed withmuch greater effectiveness than through simple pyrolysis alone. Someexamples of the potentially deleterious compounds that may be removedare: volatile organic compounds (VOCs), monoaromatics, polycyclicaromatic hydrocarbons (PAHs), heavy metals, and chlorinated compounds(e.g. dioxins and furans). A proven approach to remove these substancesis to wash the exterior surfaces with and/or rapidly infuse a solventinto the pore volume of the material targeted to remove thesesubstances. Following the infusion with either mechanical extraction,drying, or other methods to remove the solvent, laden with thesubstances in question, from the pores and interparticle spaces is adesirable, but not strictly necessary step to further reduce the levelsof toxicity. For example, the following data shows removal of dioxinsusing the treatment process of the present invention.

Raw coconut Treated coconut Raw pine Treated pine shell biochar shellbiochar biochar biochar TEQ ng/kg 0.7 0.4 9.6 0.4 (method 8290A)

Another approach for some toxic compounds (benzene as one example) is,rather than removing the compounds in question, to react them in placewith other compounds to neutralize the toxicant. This approach can beused either with washing, or forced/assisted infusion, and in thesecases a removal step is less necessary—although it still can be used toprepare the material for another, subsequent phase of treatment.

Much attention is given to the removal of toxic compounds, but it shouldbe also be noted that at times, it can be extremely beneficial toactually add or treat the material with toxic compounds. A primaryexample of this is sterilization, or preparation for selective infusion.Even after pyrolysis, residual biological life has been found topotentially establish itself in biochars given the right conditions.Treating, washing, or infusing the material with antiseptics such asmethanol, ethanol, or other antibacterial or antiviral substances can bea key step in removing contamination and preparing the material for usein microbial applications. A variation on this approach is to infuse,treat, or wash the material with a selectively toxic compound, such as atargeted antibiotic or pharmaceutical targeted towards interrupting thelifecycle of a specific set of microorganisms or organisms, therebygiving other microbes, either through infusion or merely contact in situthe opportunity to establish. Some examples of this treatment would bethe use of antifungals such as cycloheximide to suppress fungal growthand provide an environment more well suited toward the establishment ofbacteria. As has been stated previously, the methods may be used alone,or in combination with one another. Specifically, a toxic compound suchas ethanol, may be infused, removed, and then steps may be taken toremove other toxic compounds, followed by steps to add carbon sources orgrowth media.

10. Surface Structures/Crystals/Tortuosity

The physical surface and pore structure of the material is criticallyimportant to its suitability as a microbial habitat. There are manyfactors that contribute to the surface structure of the material. Themost notable of these factors is the biomass used to produce thecarbonaceous material—the cellular structure of the biomass dictates thebasic shape of many of the pores. For example, pyrolyzed coconut shellstypically have less surface area, and a more diverse distribution ofpore sizes than pyrolyzed pine wood, which, when pyrolyzed at the sametemperature, has greater surface area, but a more uniform (less diverse)pore size distribution. Tortuosity, or the amount of curvature in agiven path through a selected pore volume is also an extremely importantcharacteristic of engineered porous carbonaceous materials.

FIG. 26 shows the total fungi/bacteria ratio for two biochars derivedfrom different biochar starting materials, e.g., feedstocks. Eachbiochar was loaded with different levels of moisture, and the totalfungi/bacteria ratio was monitored during the first week. Biochar A 2301showed a constant total fungi/bacteria ratio of 0.08 across moisturelevels range 5000 ng from 15% to 40%, while Biochar B 2302 showed aconstant total fungi/bacteria ratio of 0.50 for moisture levels rangingfrom 30% to 40%. It is theorized that, a fungi/bacteria ratio between0.05 and 0.60 is an effective prescription for a stable biocharcomposition. This composition allows a commercially viable product,which has sufficient shelf life that it can be delivered to storagehouses waiting for the proper planting window.

It is theorized that the difference in the observed total fungi/totalbacteria ratios of may also be explainable by the structures of thebiochars. Biochar's having an open pore structure, e.g., moreinterconnected pores, promotes more bacteria formation; while closedpores, e.g., relatively non-connected nature of the pores, tends topromote fungi formation. Biochars with differing microbial communitiesmay be beneficial for specific applications in commercial agriculture.Thus, custom or tailored loading of the microbial population may be adesired implementation of the present invention.

For example, as shown in FIGS. 27a, 27b and 27c , Biochar A 2701 showsthat it has a greater population of, i.e., is inhabited by, more gramnegative, gram positive and actinomycetes than Biochar B 2702. Thus, forexample, Biochar A would be more applicable for use with certainagricultural crops in which Plant Growth Promoting Bacteria (PGPB)species in the actinomycetes, gram (−) pseudomonas, and bacillus groupsare used for nutrient utilization and uptake.

It should be noted that both pyrolysis and post-treatment can be used tofurther modify the shape of these pores and structures. Pyrolyzing athigher temperatures, injecting select gasses or liquids duringpyrolysis, or both typically will increase the pore volume and surfacearea of the material in question. Steam is the most readily availablegas to cause this effect, but hydrogen sulfide, carbon dioxide, carbonmonoxide, as well as other reactive gasses can be used. Prior art hasclearly shown that the surface area of a biochar changes based onfeedstock and pyrolysis temperature. Post treatment focused on a forcedinfusion of a strong acid, or other reactive substance into the porespace of the carbonaceous material can also be used to modify the poresize and pore volume of material by removing or breaking down the carbonmatrix which forms the structure of the biochar, or other porouscarbonaceous material. Acid etching or infusion can also be used to makesmoother surfaces rougher. Rough surfaces can be very useful in theattachment and immobilization of microbes. Smooth surfaces can be usefulfor the easy release of carried microbes. Coating the surface area withmaterials such as starches is a technique to make rough surfacessmoother. Ultrasound, with or without a transmission media (gel, liquid,oil, or other) can also be used to rupture interpore divisions andcreate more pore space. Flash gasification, either at atmosphericpressure, or under negative or positive pressure, of liquid infused intothe pores by the methods previously disclosed can also be used to crack,disrupt, or fracture solid material separating adjacent pores.

While much attention is given to modifying the pore structure byremoving carbonaceous material, it should be noted that the porestructure can also be modified by the coating, forced infusion, and/oraddition of materials which will bond to the carbon and consume porevolume, smooth surfaces, add tortuosity, change the exterior surfaces,or all of these. In the most simple form, it should be clear thatmaterials may be added to coat surfaces or fill pore volume eitherthrough forced infusion, simple contact, or other means. However, if thematerial is infused or even simply contacted with a super saturatedsolution of a substance that will crystallize, such as sucrose, sodiumchloride, or other common or uncommon substances known to form crystals.It should be noted that the crystals or substances used to create themdo not need to be water soluble, and in fact in many cases it isdesirable if they are not. The crystals may also be composed ofnutrients or substances which may be beneficial to microbial or plantlife. Examples of this are sucrose and monoammonium phosphate, bothknown for their ability to easily crystallize and be beneficial formicrobial and plant life respectively. By adding material or evengrowing crystals on the carbon, a hybrid material is formed which canhave many properties that are exceptionally useful for the delivery andestablishment of microbial systems. Crystallization is also way to addtortuosity to a carbonaceous material and typically is much moreeffective in this aspect than coating with solids alone.

11. Compatibility with Biofilm Formation

Biofilms can be an important factor in the survival of a microbe inextreme or challenging conditions. Bacterial communities can shift theirmorphology to increase nutritional access and decrease predation. Onesuch modification is that the bacteria may attach to surfaces, such asthose found in biochar, in a densely compacted community. In thiscompacted form, they may form an extracellular polymeric substance (EPS)matrix called a biofilm. These communities can contain hundreds ofdifferent species which find shelter under the protective EPS coatingfrom predatory protozoa, pathogens, contaminants, and otherenvironmental stressors. In some cases, usually related to public healthor healthcare, biofilms are undesirable as they typically allowpathogenic microbes to survive exposure to antiseptics, antibiotics,predatory microbes such as protozoa, or other agents which may eliminatethem or negatively impact their prospects for survival. But inagricultural settings, encouraging target biofilm establishment couldlead to improved microbe survival and thus improved agricultural or cropbenefits.

As outlined in the article titled The Effect of Environmental Conditionson Biofilm Formation of Burkholderia psudomallei Clinical Isolates, itcan be seen that certain bacteria require certain environmental factors,among them surface pH, for the creation of biofilms. See Ramli, et al.,The Effect of Environmental Conditions on Biofilm Formation ofBurkholderia psudomallei Clinical Isolates (Sep. 6, 2012)(http://dx.doi.org/10.1371/journal.pone.0044104). It is believed thatother surface characteristics (rugged vs. smooth surfaces, surfacecharge, and more), along with moisture levels and relative humidity alsoplay a large role in biofilm formation.

But for certain microbes requiring deployment into environments known topresent survival challenges, optimizing a delivery material to encouragethe formation of these protective biofilms can provide the targetedmicrobes with a significant advantage. Also, many vegetable and shortcycle row crops such as tomatoes, lettuce, and celery form mutualisticrelationships with bacteria that lead to the formation of biofilms onroot hairs that function not only in nutrient uptake but also in plantpathogen resistance.

As outlined in previous disclosure, treatment of raw biochar can be usedto adjust the surface pH to a level suitable for biofilm formation.Similarly, adjusting the humidity by selectively leaving a measured orcontrolled amount of water resident in the pore volume of the materialcan also provide benefit. Lastly, the techniques outlines for modifyingthe physical surface properties of the material either by smoothing orroughening, can be key factors also.

It should be clear that these factors can also be reversed to create anenvironment that is unsuitable for biofilm formation in applicationswhere the formation of biofilms on the carrier is not desirable—e.g.delivery or applications where quick release of microbes from thecarrier is important.

12. Surface Charge

The surface charge of a porous carbonaceous material can be cruciallyimportant in the association and establishment of targeted microbes withor on the material. For example, most bacteria have a net negativesurface charge and in certain conditions a specific bacterium may favorattachment to positively charged surfaces. In some biologicalapplications, this attachment may be preferred, in others, attachmentmay not be preferred. However, modifying the surface charge of thematerial is clearly a way to impact the suitability for attachment ofcertain microbes. There are many ways in which the surface charge of acarbonaceous material may be changed or modified. One way to accomplishthis is by treating the surface area of the material with a solutioncontaining a metal, such as Mn, Zn, Fe, or Ca. This can be performedeither by doping the material with these metals prior to or duringpyrolysis, or more preferably, by using a forced infusion or treatmenttechnique after pyrolysis to deposit these substances on the interiorand/or exterior surfaces of the carbonaceous material. By controllingthe amount and or types of substances infused, the surface charge of thematerial can be modified by encouraging loading of O₂ ⁻ or other anions,or conversely, N⁺, NH₂ ⁺, or other cations. This modification of surfacecharge can have a profound impact on the ability of certainmicroorganism to be immobilized on the interior and exterior surfaces ofthe material.

Another application of surface charge can be found by temporarilycharging the carbonaceous material during inoculation with microbes.Carbon is used as a cathode or anode in many industrial applications.Because of its unique electrical properties, carbon, or morespecifically porous carbonaceous materials, may be given a temporarysurface charge by the application of a difference in electricalpotential. One application of this mechanism is to create a temporarilypositively charged surface to encourage microbial attachment. Then,while the charge is maintained, allowing the microbes to attachthemselves to and colonize the carrier. Once the colonization iscomplete, the charge can be released and the carrier, laden withmicrobes can either be deployed as is, or can undergo further treatmentto stabilize the microbes such as lyophilization, or freeze drying.

13. Enzyme Activity

For some types of microbes, enzyme activity, or the presence of certainenzymes is every bit as important as the availability of energy ornutrition. Enzymes can be critical in the ability of microbes tometabolize nutrition, which in turn can be a key element ofreproduction, survival, and effective deployment. There are six maintypes of enzymes: hydrolases, isomerases, ligases, lyases,oxidoreductases, and transferases. These enzymes can be important inmicrobial applications. Through treatment or even simple contact,enzymes, like nutrients and energy sources, can be deposited on thesurfaces or within the pore volume of porous carbonaceous materials,either as solids, or in solution/suspension, ensuring the enzymes arenot degraded through the process. However, forced infusion of enzymesthrough the treatment processes previously outlined allows for muchgreater storage capacity and much greater levels of contact with theinterior surfaces of the biochar, and as such, is preferable to simplecontact. In some cases, the carbonaceous material can be used to deliverenzymes alone into an environment where both a habitat and enzymes areneeded to promote or encourage the growth of certain indigenousmicrobes.

Another important aspect of enzyme activity is that some bacteria makeextra-cellular enzymes which could be bound by the biochar or eitherreduce or even stop biochemical reactions. Thus, in certain situationswhen application is appropriate the carbonaceous material can be used toinhibit or make certain enzymes ineffective. For example, if the biocharis being used as a carrier for food or certain chemicals that arevulnerable to breakdown by enzymatic degradation and these specificenzymes would be bound by the biochar, then using the carbonaceousmaterial as the carrier would provide for greater shelf-life andviability of the product versus traditional carriers.

14. Sterilization

In many cases, it is desirable to remove potential unwanted microbesfrom the surfaces and pore volume of the material through sterilization.At outlined above, infusion with antiseptics or antibiotics are a way toaccomplish this. Boiling, or more preferably, forced infusion of steamis also a technique that can be used to remove resident microbial life.Heating to a temperature above 100 degrees C., and preferably between100 and 150 degrees C. is also effective for removing some microbiallife. Heating may be required for ideally 30 minutes or more, dependingon volume, method, and extent (temperature, radiation). Autoclaving canalso be used 30 minutes, 121 degrees C., 20 psig. For applicationsrequiring a high level of sterility, gamma irradiation can be used, withdosages adjusted for the level of sterility needed in ranges of 5 to 10kGy or even 50 to 100 kGy or even higher dosage levels. For allsterilization methods, the extent of treatment required will depend onthe volume of material and the required level of sterilization. Ingeneral, sterilization, using heat, should be done for at least 30minutes, but should be adjusted as needed.

At this point, it should be clear that all of these properties can becontrolled and modified to create a treated, controlled biochar that issuitable for use as a microbial carrier, delivery system, habitat,fermentation substrate, or environmental (soil, water or other)enhancement. By controlling these properties and producing a materialmatched to the application and the microbe(s) in question, effectivenesscan be dramatically improved over both traditional biological carriers,and many forms of raw, untreated, uncontrolled biochar. Furthermore,varying materials, with varying properties, may be aggregated to providedelivery systems or habitats targeted towards consortia, communities, orgroups of microbes.

E. Inoculating, Applying, or Immobilizing the Microbes on the Biochar

Typically, the prior art teaches either placing biochar on soils aloneor combining the biochar with compost and using this mixture as a soilamendment. The nature of the microbial population in this compostmixture is poorly disclosed by the prior art. Thus using more targetedmethods to get the desired microbes into the suitable habitat created bythe raw biochar, or more preferably treated or controlled biochar isdesired. The following are some but not all, methods and systems thatcan be used to inoculate, deploy, or otherwise associate microbial lifewith a treated or untreated biochar:

1. Co-Deployment

This method focuses on deploying the microbes at the same time as thebiochar. This can be done either by deploying the biochar into theenvironment first, followed by microbes or by reversing the order, oreven deploying the two components simultaneously. An example of thiswould be the deployment of a commercial brady rhizobium inoculantsimultaneously with the introduction of a treated biochar into the soilmedia. The system here is the combination use of a biochar and microbesin the environment, and more preferably a char treated to have suitableproperties for a target microbe or group of microbes which it is usedwith in a targeted application for a specified purpose, for example asymbiotic crop of said microbe(s).

In one experiment, various biochar feedstocks with variouspost-treatments were added to a soilless mix containing soybean seedsthat had been treated with a commercial microbial product containingBradyrhizobium japonicum, and compared to both a control with microbeinoculant and one without. Some of the treated biochars co-deployed withthe inoculant increased seed germination rates, one by 29%. Othersincreased nodulation measured at 10 weeks, one more than doubled thenumber of nodules. The use of the microbial inoculant increased shootbiomass in all treatments. FIG. 28 is a chart comparing shoot biomasswhen the biochar added to a soilless mix containing soybean seeds istreated with microbial product containing Bradyrhizobium japonicum, andwhen it is untreated. As illustrated in FIG. 28, shoot biomass increasedwith the biochar was treated.

FIG. 29 shows the comparison of root biomass in a microbial inoculatedenvironment versus one without inoculation. As illustrated in FIG. 29,when inoculated, root biomass decreased with the inoculant alone yetincreased with the use of all the treated biochars with or withoutinoculant.

In addition leaf tissue analysis was done which showed some of thetreated biochars co-deployed with the rhizobial inoculant showed asignificant increase in nitrogen uptake. FIG. 30 is a chart comparingthe nitrogen levels when the biochar is inoculated with the rhizobialinoculant verses when it is not inoculated. Statistical significance inthe chart in FIG. 30 is marked with a star. In all cases, nitrogenlevels increase with inoculation.

As outlined in these results, the addition of a treated biochar suitablefor co-deployment with this particular microbe increased nodulation,increased nitrogen fixation/availability, and resulted in substantiallyincreased root mass. It should be noted that to demonstrate thediffering performance of varying formulations, two formulations weretested, each showing different interactions with the microbe inquestion, along with significant variations in performance. This is justone example to demonstrate the invention of how the specific combinationof biochar feedstock, biochar treatment, co-deployed microbe, andapplication (this case plant species) can lead to improved microbialeffectiveness and thus improved results (this case plant vigor), versusno treatment, applying the microbe alone, or applying the biochar alone.Another example of co-deployment benefit could be using a biochar thathas strong absorption properties in combination with fertilizer (orinfused with fertilizer) and microbes in an agricultural setting. Thebiochar properties that help retain and then slowly release nutrientsand ions will also help the targeted microbe population to establish andgrow without being impacted by the high levels of fertilizer salts ornutrients which can often impede and sometimes kill the microbes beingdeployed.

2. Basic Inoculation

A more advanced method of inoculation centers on mixing the microbe ormicrobes in question with the treated or untreated biochar beforedeployment. In some cases, the biochar in question can be treated,produced, or controlled to assist with this deployment, making this caseslightly different than merely inoculating a microbe on untreatedbiochar. In one form, microbes suspended in liquid (either water, growthmedia, or other liquids) are deposited on the biochar and mixed togetheruntil both materials are well integrated and then the material isdeployed as a granular solid. It has been shown that materials that havebeen treated to be more hydrophilic typically accept this inoculationmore readily than hydrophobic materials—demonstrating yet another way inwhich the treatment of biochar can enhance performance. In another formof basic inoculation, the biochar is delivered in suspension in theliquid also carrying the microbes. This biochar/liquid/microbe slurry isthen deployed as a liquid. In this form, sizing the biochar particles insuch a way that their surface properties and porosity is maintained is akey element of effectiveness. Additionally, ensuring that the pores aretreated to allow easy association of both liquid and microbes with thesurfaces of the biochar is important. An example of a basic inoculationmethod of biochar for a bacteria in lab scale is as follows:

-   -   1) Isolate Pseudomonas protegens on a plate with 1.5% w/v        Tryptic Soy Broth solidified with 1.5% w/v agar and incubate at        30° C. for 12 h    -   2) Take an isolated colony of Pseudomonas protegens and grow up        in a 1.5% w/v TSB solution (90 ml) along with 10 g sterile        biochar (sterilized at 110 C in small batches for 15-20 min) and        combine both in a sterile 250 ml Erlenmeyer flask    -   3) Shake contents of flask at 150 rpm at 30° C. for 12 h, or        greater    -   4) Transfer contents of flask into a sterilized ultracentrifuge        tube (250 ml) and spin at 10,000×g for 10 min    -   5) Carefully remove supernatant liquid fraction by filtering        through a Whatman No 4 filter with a vacuum filtration system to        separate out the bulk liquid from biochar.        After basic inoculation, the material and the microbes may be        deployed immediately, stored for future use, or stabilized using        technology such as lyophilization.

3. Assisted Inoculation

Another form of inoculation, which appears to have greater efficacy withsome microbial systems, is assisted inoculation. Assisted inoculationinvolves providing mechanical, chemical, or biological assistance tomove the targeted microbe either into the pore volume of the carrier oronto interior surfaces of the material that normally may not beaccessible. Realizing that many microbes require liquid, and preferablywater, for mobility, the most straightforward method of assistedinoculation requires infiltrating the pore volume of the material withwater prior to contact with the targeted microbes. This water infusioncan be done using the treatment methods described previously in thisdisclosure. It has been shown that, with certain microbes, making thischange alone will have a positive impact on the ability of microbes toassociate with and infiltrate the material. In one experiment, it wasshown that water infusion improved release rate on both a treated pinebiochar with granular particles and with a coconut biochar powder. FIG.31 illustrates the three-day release rates of water infused biocharcompared to other types of biochar. As illustrated, results varydepending upon the biomass.

Changes can also be made in the media to reduce surface tension andincrease flowability through the addition of a surfactant to the water,either into the liquid used to carry the microbes, or into the pores ofthe material itself, through simple contact, or preferably forcedinfusion.

Additionally, the microbes themselves may be assisted into the poresusing the treatment techniques previously outlined. Care needs to betaken to match the microbe to the technique used, but many microbes arecapable of surviving vacuum infiltration if performed at relativelygentle, lower pressure differentials (+/−10% of standard temperature andpressure). Some microbes, and many spores however are capable ofsurviving vacuum infiltration even at relatively large pressuredifferentials (+/−50, 75, or even 90 or 95% or more variation fromstandard temperature and pressure). When this technique is used, aliquid mixture is constructed containing both liquid to be infused andthe microbe or microbes in question. The liquid is then used as the“infiltrant” outlined in previous disclosure related to placing liquidinto the pore volume of the material. The final material, infiltratedwith microbes, may then be heated to incubate the microbes, cooled toslow development of the microbes or stabilize the microbes, or haveother techniques applied such as lyophilization. The material may thenbe delivered in solid granular form, powdered, further sized downward bygrinding or milling, upward by agglomerating, aggregating, or bonding,or suspended in a liquid carrier. A clear advantage to this assistedinfusion approach is that the material can be processed or handled afterinoculation with more microbial stability because the targeted microbesare inhabiting the interior pore volume of the material and are lessprone to degradation due to contact with exterior surfaces, or otherdirect physical or environmental contact. This method may be appliedrepeatedly, with one or more microbes, and one to many moisture removalsteps. It may also be combined with the other inoculation methodsdisclosed here either in whole or in part.

FIGS. 32a, 32b and 32c show scanning electron microscopy (SEM) images ofraw biochar compared to ones that have been processed by being infusedunder vacuum with bio-extract containing different microbial species.

FIG. 32a is a SEM (10 KV×3.00K 10.0 μm) of pore morphology of rawbiochar. FIG. 32b is a SEM (10 KV×3.00K 10.0 μm) of pore morphology ofraw biochar of FIG. 32a after it has been infused with microbialspecies. FIG. 32c is a SEM (10 KV×3.00K 10.0 μm) of a pore morphology ofanother example of raw biochar of FIG. 32a after it has been infusedwith microbial species. The images confirm the ability to incorporatedifferent microbes into the pores of biochar by treatment. In turn,these beneficial microbes can interact with and enhance the performanceof the environment they are deployed into, for example the plants' rootsystems when the inoculated biochar is mixed with the soil in the rootzone.

Compared to a biochar that has immersed in a compost tea, which may havea relatively short, e.g., a few days for the life of the microbes, theimpregnated populations of examples of the present treated biochars, arestable over substantially longer periods of time, e.g., at least an 8week period and in some cases 1 year or more as measured byPLFA(Phospholipid-derived fatty acids) analysis. PLFA analysis extractsthe fatty acid side chains of phospholipid bilayers and measures thequantity of these biomarkers using GC-MS. An estimate of the microbialcommunity population can thus be determined through PLFA analysis. Themicrobial activity may also be inferred through PLFA analysis bymonitoring the transformation of specific fatty acids. Thus, theimpregnation of the biochar with a microbial population provides forextended life of the microbes by at least 5×, 10×, or more over simplecontact or immersion. In fact, some microbes may be better suited tosurfactant infiltration versus vacuum infiltration and vice versa andthis may impact the shelf life, penetration, viability, or othercharacteristics of the microbes.

As used herein, unless stated otherwise, the stable shelf life of anexample of a biochar product having a microbial population is the periodof time over which the product can be stored in a warehouse, e.g., dryenvironment, temperature between 40° F.-90° F., with a less than 50%decrease in microbial population.

4. Integrated Growth/Deployable Substrate

With many microbes, especially fungi, it can be helpful to develop or“grow” the microbes on the material itself. With porous materials,rather than mechanically or chemically assisting the infiltration of themicrobes, it can be beneficial to allow the microbes themselves toinhabit the pore volume of the material prior to deployment. In fact,with materials constructed to effectively immobilize microbes, this canbe the most efficient technique to stabilize, store, and ultimatelydeploy the microbes in question.

An example of this method involves preparing the biochar material forthe microbes, sometimes through thorough cleansing, other times throughaddition of either enzymes or energy sources needed by the microbe inquestion, preferably using the treatment techniques described previouslyin this disclosure. Once the material is prepared, the microbes areplaced onto the material, or infused into the material and thenincubated for a period of time. In the case of many microbial systems,the microbes themselves will inhabit the material and form closeaffiliations with available surfaces and pore volume. At this point, thematerial can be deployed with the microbes actively attached andaffiliated. With many microbes, especially fungi, this is a preferredmethod of deployment and shows many advantages over co-deployment, orbasic inoculation because of the tight integration of biological lifewith the material itself.

An example of an integrated growth inoculation method of biochar for afungus in lab scale is as follows:

-   -   1) Make petri dishes containing corn meal agar (17 g/L), glucose        (10 g/L), and yeast extract (1 g/L)    -   2) Inoculate plates with Sordaria fimicola and incubate between        22-30 C for at least 1 day to produce hyphae    -   3) Sterilize an inoculating loop and slice “plugs” of the hyphae        and agar generating cubes that are agar and hyphal mass    -   4) Inoculate a sterile plate with a “plug” in the center of the        plate, around perimeter have sterile biochar    -   5) Incubate plate for at least a day and remove biochar (that        are now covered with grown over hyphae)]

It should be noted that because of this effect, biochars, andspecifically treated biochars can also be extremely effective substratesfor solid state fermentation—particularly when growth media or energysources are added to the pore volume of the material. So, onceincubation is ongoing, the material can either be removed, with theintegrated microbes, and deployed, or it can be stabilized for long termstorage, or it can be left in situ and used as a fermentation or growthsubstrate to develop or grow more microbes—especially those that requirea solid to propagate and develop.

5. Media and/or Enzyme Infiltration

As mentioned previously, growth media, energy sources, enzymes, or otherbeneficial/necessary components for microbial growth may be infused intothe pore volume or coated onto the surfaces of the material in question.This method can be combined with any of the other inoculation techniquesdisclosed here. It has been shown that with certain microbes and certaintypes of material, inoculation with growth media or enzymes cansignificant impact the effectiveness of the biochar material as acarrier.

6. Habitat Pre-Establishment (Enhanced Rhizosphere)

There are certain microbes which, because of symbiotic associations withhost organisms, such as plants, prefer to develop in the vicinity of theorganism, such as the active root or other plant tissue. An effectivemethod for deploying these organisms can be to develop and deploy theplant/microbe/habitat (biochar) system together as a unit.

An example of this is germinating seed or transplanting a seedling ordeveloping juvenile plant in the presence of treated or untreatedbiochar, and the targeted microbes. Biochar that has been treated toencourage hydrophilicity and neutral pH typically allows for easieraffiliation of plant root tissue with the material. As this affiliationoccurs, a habitat for symbiotic organisms is developed within thematerial itself due to the proximity of active plant tissue to microbesreliant on the tissue for energy. As this symbiosis continues, thenumber, activity, and colony size of the targeted microbes will continueto grow. At this point, the plant and biochar can be deployed togetherinto the target environment, acting as a pre-established habitat andcarrying the microbes along with them.

Another option is to develop and then remove the biochar from the“incubation” system either by stripping the biochar material from thesymbiotic organism, such as the root mass, or by sieving or sifting themedia used to grow the plant. At this point, the microbes can either bedeployed directly or stabilized for storage.

Thus, through more controlled inoculation of the biochar particles, onecan achieve a predetermined and controllable amount of a microbialcommunity, e.g., population, into the soil. This integration of amicrobial community with a biochar particle, and biochar batchesprovides the ability to have controlled addition, use and release of themicrobes in the community. In agricultural applications, thisintegration c a n further enhance, promote and facilitate the growth ofroots, e.g., micro-roots, in the biochar pores, e.g., pore morphology,pore volume.

Other methods than those listed above exist for integrating a microbialcommunity with an untreated or previously infused biochar particle.Different manners and methods would be preferred depending on needs tominimize contamination, encourage biochar porecolonization/infiltration, minimize labor and cost and producing auniform, or mostly uniform, product.

Other methods for integrating a microbial community with a biocharparticle may include, but are not be limited to the following: whileunder vacuum, pulling the microbial solution through a treated biocharbed that is resting on a membrane filter; spraying a microbial solutionon top of a treated biochar bed; lyophilizing a microbial solution andthen blending said freeze dried solution with the treated biochar; againinfusing, as defined previously, the treated biochar with a microbialsolution; adding treated biochar to a growth medium, inoculating withthe microbe, and incubating to allow the microbe to grow in said biocharcontaining medium; infusing, as defined previously, the biochar with afood source and then introducing the substrate infused biochar to amicrobe and incubating to allow the microbes to grow; blendingcommercially available strains in dry form with treated biochar; addingthe treated biochar to a microbial solution and then centrifuging at ahigh speed, potentially with a density gradient in order to promote thebiochar to spin down with the microbes; densely packing a column withtreated biochar and then gravity flowing a microbial solution throughthe column and possibly repeating this multiple times; or adding themicrobe to a solution based binder that is well known to enter thetreated biochar pores and then adding said solution to the treatedbiochar. In order to insure the proper microbial community the treatedbiochar may need to be sterilized prior to these methods for integratinga microbial community. All or parts of the above manners and methods maybe combined to create greater efficacy. In addition, those skilled inthe art will recognize that there may be additional manners or methodsof infusing biochars with microbials, including those created by thecombination of one or more of the manners and methods listed above,without departing from the scope of the present invention.

F. Using Microbial Inoculated Biochars

Thus, treated biochar can have a microbial community in its pores(macro-, meso-, and combinations and variations of these), on its poresurfaces, embedded in it, located on its surface, and combinations andvariations of these. The microbial community can have several differenttypes, e.g., species, of biologics, such as different types of bacteriaor fungi, or it may have only a single type. For example, a preferredfunctional biochar, can have a preferred range for bacterial populationof from about 50-5000000 micrograms/g biochar; and for fungi, from about5 to 500000 micrograms/g biochar. A primary purpose in agriculturalsettings, among many purposes, in selecting the microbial population islooking toward a population that will initiate a healthy soil, e.g., onethat is beneficial for, enhances or otherwise advance the desired growthof plants under particular environmental conditions. Two types ofmicrobial infused biochars will be discussed further for agriculturalsettings: bacteria and fungi. However, the microbes may also be used inother applications, including but not limited to animal health, eitherdirectly or through interactions with other microbes in the animals'digestive tract and public health applications, such as microbiallarvicides (e.g. Bacillus thuringiensis var. israelensis (Bti)) andBacillus sphaericus used to fight Malaria).

G. Bacteria Inoculated Biochars

PGPB include, for example, plant growth promoting rhizobacteria,free-living and nodule-forming nitrogen fixing bacteria, organicdecomposers, nitrifying bacteria, phosphate solubilizing bacteria,biocontrol agents, bioremediation agents, archea, actinomycetes,thermophilic bacteria, purple sulfur bacteria, cyanobacteria, andcombinations and variations of these.

PGPB may promote plant growth either by direct stimulation such as ironchelation, phosphate solubilization, nitrogen fixation and phytohormoneproduction or by indirect stimulation, such as suppression of plantpathogens and induction of resistance in host plants against pathogens.In addition, some beneficial bacteria produce enzymes (includingchitinases, cellulases, −1,3 glucanases, proteases, and lipases) thatcan lyse a portion of the cell walls of many pathogenic fungi. PGPB thatsynthesize one or more of these enzymes have been found to havebiocontrol activity against a range of pathogenic fungi includingBotrytis cinerea, Sclerotium rolfsii, Fusarium oxysporum, Phytophthoraspp., Rhizoctonia solani, Pythium ultimum.

Currently the most economic conventional solid carrier used to delivermicrobes is peat. A solid carrier allows for a relatively long shelflife and a more direct application to a plant's root system compared toa microbial liquid solution, which would be sprayed directly.

Research has shown a substantial increase in PGPB growth anddistribution resulting from being infused in biochar. For example, dataresulting from research conducted to compare the effects upon CO2production (an indicator of bacterial growth) using peat and biocharsshow the beneficial effects of using various biochars in promoting PGPBgrowth. As illustrated in the left-hand chart in FIG. 33, peat resultsin CO2 production of between approximately 10% and 30% (depending uponthe grown medium), whereas biochars result in CO2 production ofapproximately 48% and 80%. Replicated experimental results usingdifferent biochars confirm CO₂ production of approximately 30% to 70%(depending on the grown medium), as compared to approximately 10% to 20%for the peat control.

The method developed for determining this CO2 production as an indicatorof bacterial growth consists of the following. The substrate, herebiochar or peat, is sterilized by heating at 110 C for 15 hours. Abacterial stock solution is then created, here Tryptic Soy Broth wassolidified with agar at 1.5% w/v in petri plates to isolate the gramnegative non-pathogenic organism Escherichia coli ATCC 51813 (15 hgrowth at 37° C.). Then an isolated colony is captured with aninoculating loop and suspend in 10 ml sterile buffer (phosphate buffersaline or equivalent) to create the bacterial stock solution. Lactosecontaining assays are then used, here, test tubes that contain 13 ml ofeither Lauryl Tryptose Broth (LTB) or Brilliant Green Broth (BGB) thatalso contain a Durham tube. A negative control is generated by adding 10μL of sterile buffer to triplicate sets of LTB and BGB tubes. A positivecontrol is generated by adding 10 μL of bacterial stock solution totriplicate sets of LTB and BGB tubes. A negative substrate is generatedby adding 1.25 ml (˜1% v/v) of sterile substrate to triplicate sets ofLTB and BGB tubes. A positive substrate is generated by adding 1.25 ml(˜1% v/v) of sterile substrate and 10 μL of bacterial stock solution totriplicate sets of LTB and BGB tubes. The tubes of the four treatmentsare then incubated statically in a test tube rack at 37° C. for at least15 h. The tubes are then carefully observed and any gas bubbles capturedby the Durham tube within respective LTB or BGB tubes are closelymeasured with a ruler. Small bubbles <0.2 mm should not be considered. Acontinuous bubble as shown in individual tubes in FIG. 34 are what areobserved and quantified. FIG. 34 is an example of carbon dioxideproduction captured as a continuous gas bubble in BGB (left two tubes)and LTB (right two tubes) growth medium. The percent carbon dioxideproduction is then calculated by dividing the recorded bubble length bythe total Durham tube length and multiplying by 100.

Further tests were conducted using the Streptomyces lidicus WYEC 108bacterium found in one of the commercially available products sold underthe Actinovate brand. Actinovate products are biofungicides that protectagainst many common foliar and soil-borne diseases found in outdoorcrops, greenhouses and nurseries. The formulations are water-soluble.

FIG. 35 illustrates the effects upon the growth of Streptomyces lidicususing conventional peat versus biochars. In the test illustrated by thephotograph on the left of FIG. 35, an Actinovate powder was blended withpeat, placed in an inoculated media and incubated at 25° C. Thephotograph shows the distribution and density of white colonies after 3days. In the test illustrated by the photograph on the right of FIG. 35,an Actinovate powder was blended with the treated biochar, placed in aninoculated media and incubated at 25° C. The photograph also shows thedistribution and density of white colonies after 3 days, thedistribution and density of which are significantly greater than thoseachieved with peat.

FIG. 36 further illustrates the improved growth of the Actinovatebacterium using biochar versus peat. The left photograph shows onlylimited and restricted growth away from the peat carrier. The rightphotograph shows abundant growth of the bacterium spread much fartherout from the biochar carrier.

Another application of using biochar inoculated with bacteria would bein the biofuel industry, where methanotroph inoculated biochar could beused to create methanol. Methanotrophic bacteria are proteobacteria withdiverse respiration capabilities, enzyme types, and carbon assimilationpathways. However, Methylosinus trichosporium OB3b is one of the fewmethanotrophs that can be manipulated by environmental conditioning toexclusively produce methanol from methane. M. trichosporium OB3b is oneof the most well studied aerobic C₁ degraders and can be grown in eitherbatch or continuous systems. As mentioned earlier, the large pore volumeand surface area of biochar is suitable for bacterial colonization andshould subsequently increase substrate access to enzyme activationsites. To improve the conversion rate, copper, nitrate, and phosphateshould be included in the system. The use of biochar as a supportmaterial for the aerobic bioconversion of methane to methanol provides apore distribution suitable for both adsorptions of methane andimpregnation with bacteria. By providing biological and adsorptivefunctionality the biochar can intensify the bacteria in the biochar andincreases the conversion rate.

In general, bacteria communicate via the distribution of signalingmolecules which trigger a variety of behaviors like swarming (rapidsurface colonization), nodulation (nitrogen fixation), and virulence.Biochars can bind signaling molecules and in particular it is believedcan bind a major signaling molecule to their surface. This bindingability can be dependent upon many factors including on the pyrolysistemperature. This dependency on pyrolysis temperature and other factorscan be overcome, mitigated, by the use of examples of the present vacuuminfiltration techniques. For example, a signaling molecule that isinvolved in quorum sensing-multicellular-like cross-talk found inprokaryotes can be bound to the surface of biochars. Concentration ofbiochars required to bind the signaling molecule decreased as thesurface area of biochars increased. These signaling molecules may beadded to the surface of a biochar and may be used to manipulate thebehavior of the bacteria. An example of such a use would be to bind themolecules which inhibit cell-to-cell communication and could be usefulin hindering plant pathogens; using techniques in the present inventionsignaling molecules may be added to the surface of a biochar to engineerspecific responses from various naturally occurring bacteria.

H. Fungi Inoculated Biochars

Beneficial fungi include, for example, saprotrophic fungi, biocontrolfungi, ectomycorrhizae, endomycorrhizae, ericoid mycorrhizae, andcombinations and variations of these. It is further theorized that, ingeneral, biochars with greater fungal development may be better suitedfor perennial crops such as grapes, almonds, blueberries, andstrawberries in which symbiotic relationships with arbuscularmycorrhizal fungi (AMF) are favored over PGPBs. The presence of highconcentrations of AMF spores in biochars can therefore rapidly promotefungal colonization of plant root hairs leading to extensive mycelialdevelopment. Increased plant root associations with mycelial filamentswould consequently increase nutrient and water uptake.

Mycorrhizal fungi, including but not limited to Endomycorrhizae andEctomycorrhizae, are known to be an important component of soil life.The mutualistic association between the fungi and the plant can beparticularly helpful in improving plant survivability in nutrient-poorsoils, plant resistance to diseases, e.g. microbial soil-bornepathogens, and plant resistance to contaminated soils, e.g. soils withhigh metal concentrations. Since mycorrhizal root systems significantlyincrease the absorbing area of plant roots, introducing mycorrhizalfungi may also reduce water and fertilizer requirements for plants.

Typically mycorrhizae are introduced into soil as a liquid formulationor as a solid in powder or granular form and contain dormant mycorrhizalspores and/or colonized root fragments. Often the most economic andefficient method is to treat the seeds themselves, but dealing withtraditional liquid and powder inoculums to coat the seed can bedifficult. In accordance with the present invention, inoculated biocharmay be used to coat the seeds by, for example, using a starch binder onthe seeds and then subjecting the seeds to inoculated biochar fines orpowder. Another method is by placing the mycorrhizae inoculum in thesoil near the seeding or established plant but is more costly and hasdelayed response as the plants initial roots form without a mycorrhizalsystem. This is because the dormant mycorrhizae are only activated whenthey come close enough to living roots which exude a signaling chemical.In addition if the phosphorus levels are high in the soil, e.g. greaterthan 70 ppm, the dormant mycorrhizae will not be activated until thephosphorus levels are reduced. Thus applying inoculant with or nearfertilizers with readily available phosphorus levels can impede thedesired mycorrhizal fungi growth. A third option is to dip plant rootsinto an inoculant solution prior to replanting, but this is costly as itis both labor and time intensive and only applicable to transplanting.

If the colonization of mycorrhizae can be quickened and the density ofthe mycorrhizae's hyphal network can be increased then the beneficialresults of mycorrhizal root systems, e.g. increased growth, increasedsurvivability, reduced water, and reduced fertilizer needs, can berealized sooner. Prior art shows that compost, compost teas, humates,and fish fertilizers can improve microbial activities and in more recentstudies have shown physically combining arbuscular mycorrhizal fungi(AMF) inoculant with raw biochar has resulted in additional plant yieldcompared to each alone. See Hammer, et. al. Biochar Increases ArbuscularMycorrhizal Plant Growth Enhancement and Ameliorates Salinity Stress,Applied Soil Ecology Vol 96, November 2015 (pg. 114-121).

An ideal carrier for the mycorrhizae would have moisture, air, a neutralpH, a surface for fungi to attach, and a space for the roots and fungito meet. Thus a previously infused biochar created by the methoddisclosed above would be a better carrier than raw biochar alone. Theinfused biochar could be physically mixed with a solid mycorrhizal fungiinoculant or sprayed with a liquid mycorrhizal inoculant prior to orduring application at seeding or to established plants. Additionally,the infused biochar and mycorrhizal fungi inoculant could be combined toform starter cubes, similar to Organo-Cubes, rockwool, oasis cubes, andpeat pots.

The infused biochar could be further improved upon by initially infusingor further infusing the biochar with micronutrients for mycorrhizalfungi, for example but not limited to humic acid, molasses, or sugar.The growth nutrient infused biochar would further expedite thecolonization of the mycorrhizal fungi when physically combined with theinoculant and applied to seeds or plants.

Another improvement to the infused biochar would be to initially infuseor further infuse the biochar with the signaling molecules ofmycorrhizal fungi. The signaling molecule infused biochar would furtherexpedite the colonization of the mycorrhizal fungi when physicallycombined with the inoculant and applied to seeds or plants, as it wouldbring the mycorrhizae out of dormancy quicker and thus establish themycorrhizal root system quicker.

Another method for establishing and improving mycorrhizal fungi colonieswould be by growing mycorrhizae into the infused biochar and thenapplying the mycorrhizal fungi inoculated biochar to seeds or plants.Similar to a sand culture (Ojala and Jarrell 1980http://jhbiotech.com/docs/Mycorrhizae-Article.pdf), a bed of infusedbiochar is treated with a recycled inoculated nutrient solution bypassing it through the bed multiple times.

I. Batch Treatment/Bulk Production

As demonstrated above, the treatment processes described above areparticularly well suited for large scale production of biochar. Theprocesses and biochars of the present invention provides a uniquecapability to select starting materials and pyrolysis techniques solelyon the basis of obtaining a particular structure, e.g., pore size,density, pore volume, amount of open pores, interconnectivity,tortuosity, etc. Thus, these starting materials and processes can beselected without regard to adverse, harmful, phytotoxic side effectsthat may come from the materials and processes. This is possible,because the infiltration steps have the capability of mitigating,removing or otherwise address those adverse side effects. In thismanner, a truly custom biochar can be made, with any adverse sideeffects of the material selection and pyrolysis process being mitigatedin later processing steps.

Further, the processes are capable of treating a large, potentiallyvariable, batch of biochar to provide the same, generally uniform,predetermined customized characteristics for which treatment wasdesigned to achieve, e.g., pH adjustment. Treatment can result intreated biochar batches in which 50% to 70% to 80% to 99% of the biocharparticles in the batch have same modified or customized characteristic,e.g., deleterious pore surface materials mitigated, pore surfacemodified to provide beneficial surface, pore volume containingbeneficial additives.

Accordingly, the ability to produce large quantities of biochar having ahigh level of consistency, predictability and uniformity, providesnumerous advantages in both large and small agricultural applications,among other things. For example, the ability to provide large quantitiesof biochar having predetermined and generally uniform properties willfind applications in large scale agriculture applications. Thus, treatedbiochar batches from about 100 lbs up to 50,000+lbs and between may havetreated biochar particles with predetermined, uniform properties.

As the treated biochar batches are made up of individual biocharparticles, when referring to uniformity of such batches it is understoodthat these batches are made up of tens and hundreds of thousands ofparticles. Uniformity is thus based upon a sampling and testing methodthat statistically establishes a level of certainty that the particlesin the batch have the desired uniformity.

Thus, when referring to a treated batch of biochar as being “completelyuniform” or having “complete uniformity” it means that at least about99% of all particles in the batch have at least one or more property orfeature that is the same. Same being within appropriately set tolerancesfor said property. When a treated batch of biochar is referred to as“substantially uniform” or having “substantial uniformity” it means thatat least about 95% of all particles in the batch have at least one ormore property or feature that is the same. When a treated batch ofbiochar is referred to as “essentially uniform” or having “essentialuniformity” it means that at least about 80% of all particles in thebatch have at least one or more property or feature that is the same.The batches can have less than 25%, 20% to 80%, and 80% or moreparticles in the batch that have at least one or more property orfeature that is the same. Further, the batches can have less than 25%,20% to 80%, and 80% or more particles in the batch that have at one,two, three, four, or all properties or features that are the same.

J. Aggregate Biochar Particles

It has been discovered that the same benefits can be achieved throughthe production and application of biochar aggregate particles as biocharparticles that have not been aggregated. The creation of biocharaggregate particles, however, allows for easier product distribution forin various applications including industrial agricultural equipment, andprovides a highly beneficial use for the biochar dust and fines, whichare generally discarded. In this same manner, biochar aggregateparticles may be produced for use for consumption by animals or use incomposting.

The biochar, prior to being formed into a solid aggregate (e.g., throughagglomeration, extrusion, or pelletization), may be raw or treated, asdescribed above. If the biochar is treated, not only can variouscharacteristics including pH be adjusted as needed, but fertilizers,nutrients, vitamins, supplements, microbes or other additives may beinfused into the biochar prior to aggregation. (as further describedbelow). However, regardless of whether the biochar is raw or treated,the present application for biochar aggregate particles can be utilizedfor both.

There are various types of aggregation methods and resulting aggregateparticles. FIGS. 37a, 37b and 37c shows three resulting aggregateexamples. FIG. 37a shows pellets, FIG. 37b shows extrudates and FIG. 37cshows biochar sulfate prills.

As an example, one method to produce biochar aggregate particles isdepicted in the flow diagram shown in FIG. 38. The flow diagram 3800 ofFIG. 38 is an example of one method that may be used for producingbiochar aggregate particles. In general, the method of producing biocharaggregate particles from biochar may be accomplished by first collectingthe treated or untreated biochar fines at step 3802. The fines may becollected by washing the biochar media, which may cause the biocharfines and dust to be placed in suspension in the liquid solution used towash and/or treat the biochar. The biochar fines can also be produced bygrinding, crushing, sieving, or otherwise resizing biochar of a largerparticle size to one better suited for extrusion, compression,coagulation, or other forms of pelletization.

For example, the biochar fines may be separated from larger biocharparticles by dry-sieving to remove the fine particles followed bywet-sieving with deionized water to remove fine fractions that remained.To separate particles of 0.5 mm or less of equivalent diameter, both thedry-sieving and wet-sieving may be carried out with a US size 35 meshsieve. Biochar fines or dust may also be created by mechanical meanssuch as grinding cutting or crushing the raw or treated biocharparticles. These mechanically created small particles can be separatedas set forth above through sieving or may be collected by washing ortreating the material and using the resulting solution to recover thesmaller particles. The recovery of small biochar particles from thesolution can be accomplished by using chemical or physical means ofseparation or even a combination of multiple chemical and physicalseparation methods or steps.

While the biochar particles or fines may be treated in advance ofcollection, it is also possible to treat them once collected or as partof the collection process. Optionally, other physical and chemicalproperties may be adjusted during the treating step, as needed, or maybe adjusted prior to, or during the fines collection process. Forexample, the biochar fines may be collected during treatment of thebiochar media (e.g., to adjust the pH). The fines may then be collectedin the treating solution by adding a flocculent and/or coagulant to thetreating liquid, which creates a biochar slurry (the “flocculentslurry”).

Given the application, it may be necessary to de-water the flocculentslurry before further treatment, as part of the collection process. Theflocculent slurry is de-watered, typically using a belt filter press tocreate a biochar paste. Those skilled in the art will recognize thatother de-watering systems, besides a belt filter press may be used tode-water the biochar slurry and that mechanisms other than a flocculent,such as filtration, settling, or other separation technology, may beused to separate the biochar from the minerals, inorganic compounds, andother substances found in the slurry that remain in the washing ortreating solution.

Once the biochar fines are collected, a binder is then added to thebiochar particles at step 3804. The binder solution used to coagulatethe fines may be prepared by mixing a starch, polymer, lignin, clay, orother binder with water or appropriate solvents. The addition of thebinder solution creates a biochar slurry or a paste (the “binderslurry”). The binder solution may be prepared by mixing, for example,enough corn starch with deionized H₂O to create a solution. For example,the starch may be approximately 2% by weight, but may range from 0.5% to10% by weight. Those skilled in the art will recognize that anothermaterial, besides corn starch may be used as a binder. Additionally,other binders may be used with the restriction that they must beappropriate for the application they will be used in. So for example,they may not be toxic in the quantities used in agriculture or animalfeed and must be suitable for introduction into whatever applicationwithout profound ill effect. Some examples of other generally non-toxicbinders that may be used are gelatins, cellulose, sugars, orcombinations thereof. While the above describes adding the binder afterthe flocculent slurry is dewatered, the binder may also be added to theflocculent slurry before de-watering.

Like the flocculent slurry, the binder slurry is also de-watered beforefurther treatment, step 3806. The binder slurry may be de-watered usinga belt filter press to create a biochar paste. Those skilled in the artwill recognize that other de-watering systems, besides a belt filterpress may be used to de-water the biochar.

Optionally, other growth or beneficial additives may also be added tothe slurry at step 3706. The binder and the growth additives may beadded together or at separate stages, before or after the de-wateringstep 3806, with or without de-watering between, depending upon theapplication, the binder and the additives. In either event, the biocharis de-watered at step 3806 prior to further treatment.

Such growth enhancing additives may include, but are not limited to,fertilizers and beneficial microbes that can withstand the biocharaggregation process. For certain additives, the temperature of theprocess may need to be adjusted to avoid, for example, the denaturing ofthe proteins. Such additives can be added to the biochar particles(either with or after de-watering the starch slurry) through mixing. Ifa fertilizer is desired, the fertilizer may be pulverized to prepare foraddition. The fertilizer may be pulverized to an average particle sizeof <1 mm before dispensing. Liquid fertilizers may also be used insolution. For example, 1000 ppm NO₃ ⁻ N fertilizer solution may be used.Examples of fertilizers that may be added to the paste, include, but arenot limited to the following: ammonium nitrate, ammonium sulfate,monoammonium phosphate, ammonium polyphosphate, Cal-Mag fertilizers ormicronutrient fertilizers. Other additives, such as fungicides,insecticides, nematicides, plant hormones, beneficial microbial spores,secondary signal activators, vitamins, medications, supplements, orsensory enhancers may also be added to the paste in a similar manner asa fertilizer, the inclusion of which does not depart from the scope ofthe invention. Additionally, beneficial macro- and micro-nutrients suchas nitrogen, phosphorous, potassium, calcium, magnesium, sulfur, boron,zinc, iron, manganese, molybdenum, copper and chloride can be added tothe mixture at this time.

Examples of compounds, in addition to fertilizer, that may be blendedwith, infused into the pores of or coated on the surface of the biocharinclude, but are not limited to: 2,1,3-Benzothiadiazole (BTH), aninducer of systemic acquired resistance that confers broad spectrumdisease resistance (including soil borne pathogens); signaling agentssimilar to BTH in mechanism or structure that protects against a broadrange or specific plant pathogens; biopesticides; herbicides; andfungicides.

As noted above, all the above additives may also be added at varioussteps in the described processes, including with the flocculant orcoagulant, with the binder, or prior to the creation of the slurry orbiochar paste. Such additives may be added through a pre-treatmentprocess, such as those treatment processes described above (e.g., vacuuminfiltration or surfactant treatment), or other treatment processes thatresult in the infusion of liquids and/or vapors into the pores of thebiochar. It may also be possible to contact the biochar aggregateparticles, once they are produced, with additives. Such contact orcoating after production of the biochar aggregate particles is withinthe scope of the present invention.

Once de-watered, at step 3806, the biochar particles become a thickerslurry or paste (the “biochar paste”). The biochar paste, now includinga binder and possibly other additives, is then formed into solid shapes,at step 3808 and then dried, at step 3810. To form the biochar pasteinto solids, alternative forms of processing may be used. For example,the paste may be passed through an extruder, a pelletizer, a briquetter,a granulator and/or other heating, cooling, dehydration, or pressuresystem capable of forming the paste into solid shapes. Alternatively,the biochar may be mixed with the binder, both in a dry form, and thenfed into the equipment used to form the solid shaped biochar aggregateswhile adding moisture and/or other additives.

In one example of an implementation, the biochar paste is shaped throughan extruder that is heated at a temperature of 25-120° C. in order toadequately activate the starch or other binder. The extruder may bespecifically set depending on the appointed application to produce anextrudate size, ranging from 1 to 5 mm in diameter. At step 3810, theresulting extrudates are dried using a hot air, tunnel oven dryer, orother dryer known to the art. For some application, e.g., when microbesare added to or inoculated into the biochar particles, it may not bedesirable to use heat to activate the binder. Alternatively, lipids orother binders that bind at cold temperatures may be used, with thesubstitution of cooling equipment in place of heating equipment toactivate said binder.

The biochar aggregate particles from the extruder may be cut intopredetermined specific sized particles, which may take the form ofpellets. The steps of extruding and cutting may be performed together bythe extruder, or separately, again depending upon the application andequipment capabilities. In addition larger extrudates can be formedcreating a biochar spike, which can be applied by pushing them into soilnear existing plants or trees.

In one example of an implementation, the biochar aggregate particles maybe created from pyrolyzed wood or cellulosic biomass, as describedabove. The resulting biochar fines or dust are then removed from theother biochar particles at step 3802. As part of the collection process,the fines may optionally be washed with a treatment solution, asdescribed in detail above. The treatment solution may, for example, beadded to neutralize the biochar pH levels, as needed, depending upon thepH of the biochar fines. A neutralized biochar slurry is then exposed toa de-watering station and a flocculent is added to coagulate the finesor dust for de-watering. To dewater the flocculent slurry, a belt filterpress or other equipment known to the art may be used. Once dewatered, astarch or another suitable binder is added to the biochar particles, atstep 3804. Other additives may also be added to the biochar particlesduring this step. The biochar particles are again de-watered at step3806 and the slurry becomes a thicker slurry or paste. The de-wateredbiochar paste may then be formed into aggregate solids at step 3808, by,for example, the use of an extruder. The aggregate particles are thendried using a hot air, tunnel oven dryer, or other dryer known to theart, at step 3810. The aggregate particles could also be freeze dried(e.g., lyophilized) and/or allowed to air dry, at step 3810. Such dryingcan be done before or after the biochar paste is subjected to a formingprocesses.

Treatment of biochar fines or dust is optional, but may be desired forpH adjustment and/or removal of elemental ash and other harmful organicsor materials, as described in more detail above. Depending on thechemical properties of the biochar dust or fines, either water or acidicacid can be used to adjust the pH to neutral levels, and obtain aneutralized biochar slurry. The wash may also contain a surfactant ordetergent to aid in the penetration of the wash solution into the poresof the char. Those skilled in the art will recognize that other pHadjusting agents, besides acidic acid may be used to neutralize thebiochar pH levels. Additionally, other binders may be used with therestriction that they must be suitable for introduction into theirparticular application, for example not phytotoxic for use in soil ortoxic to animals or humans for use in animal feed or maintenance. Someexamples of these other pH adjustment agents include, but are notlimited to gypsum, sulfur, lime, or combinations thereof. As set forthearlier, treatment can be performed on the fines or on the largerbiochar media from which the fines are collected.

The above illustrated example details only one method of how biocharaggregate particles may be produced. As noted above, alternate formingprocesses may also be used besides passing the biochar paste through anextruder, such as a pelletizer, a briquetter, a granulator and/or otherheat, cold, evaporation and/or pressure system capable of forming thepaste into solid shapes.

Further, in another implementation, raw or treated biochar fines and/orlarger biochar particles may be dried and ground to a smaller particlesize or powder. The biochar powder can then be mixed with a binder in arotary drum to create reasonably uniform spherical biochar aggregateparticles.

Further, in another implementation, the biomass, prior to pyrolysis, maybe formed into solids shape aggregates, such as pellets, by equipmentdesigned to create pellets, granules and/or briquettes. Further, thesepellets may be stabilized by mixing a dry binder or a binder solutionwith biomass prior to pelletizing to improve the mechanical stability ofthe formed pellet. These binders may include but are not limited tostarches, polymers, clays, or lignins. By shaping the biomass prior topyrolysis, the biomass may retain the solid shape. Depending upon thebiomass, the biomass aggregate may need to be treated prior to pyrolysisto maintain the original shape with, for example, a binder solution. Wetformed, or solution treated pellets may require drying before handlingand pyrolysis. This drying may be done using hot air, a tunnel ovendryer, or other dryer known to the art.

In creating biochar aggregates, it is critical to determine the properbiochar particle size and the proper method to use to create saidparticles for the biochar aggregate production. Setting the correct sizelimits and method will ensure the aggregates maintain the physical andchemical characteristics that make the specific biochar effective in thetarget application. FIGS. 39 and 40 show SEM photos from two differentbiomass based treated biochars. FIG. 39 shows the effect of size andgrinding on particle structure for three different particle size ranges:0.1-0.3 mm, 0.05-1 mm, and <0.05 mm. These particles were collectedusing two different methods: (i) sieving the as is treated biochar and(ii) grinding the as is treated biochar and then sieving. FIG. 39 showsone treated biochar (“treated biochar 1”) and FIG. 40 shows a secondtreated biochar (“treated biochar 2”). In the treated biochar 1 SEMphotos (FIGS. 39 a, b, c, d, e and f), it is clear that the two methodsof collection show no substantial difference in pore structure. It isalso clear that the particle structure is destroyed once the particlesizes are less than 0.05 mm. In the treated biochar 2 SEM photos (FIGS.40 a, b, c, d, e and f), a different observation is noted, when thematerial is just sieved to 0.3-0.5 mm range, the biochar particle hasretained its porous structure, but when the as is treated biochar 2 isground using a medium grind or a fine grind and then sieved to 0.3-0.5mm range, then the porous structures have been mostly destroyed. FIGS.40d, 40e and 40f are zoomed images of FIGS. 40a, 40b and 40 c.

In addition, various particle size ranges from the two treated biocharswere further tested to see how biochar characteristics changed withparticle size. FIGS. 41 a, b, c and d show the effect of size fractionon four properties, water holding capacity, pH, Cl− concentration, andelectrical conductivity of two different biomass based treated biochars.For treated biochar 1, these properties, except pH, were stable acrossparticle sizes except when the particles were smaller than 0.1 mm. Thisis likely due to the loss of pore structure somewhere below 0.1 mm forthis treated biochar. For treated biochar 2, some properties, electricalconductivity and chloride concentration, seemed to correlate to particlesize in a similar way to that of treated biochar 1. But decreasingparticle size of treated biochar 2 had the opposite effect on waterholding capacity and pH versus treated biochar 1.

These observations show how particle size and the method used to createthem can have significant impact on both the pore structure of theparticles and the biochars properties. Thus an aggregate's propertiesand effectiveness can be maintained, adjusted, or harmed based on themethod for creating and collecting sized biochar particles in additionto the method of aggregation and may differ based on the biocharfeedstock and pyrolysis method.

Further in another implementation, the biomass may be sized prior topyrolysis so that the aggregate can be made with the as is biocharparticles or treated biochar particles without additional sizing.Eliminating the need to size the biochar further, may help to maintainthe biochar properties when aggregating as biochar pore structures thatare susceptible to being destroyed during sizing post pyrolysis will notbe harmed using this method.

As noted above, the biochar aggregate particles can be created witheither raw biochar or treated biochar that is treated in the manner ormethod further described below. Biochar aggregate particles can beapplied through a wide range of devices, including agriculturalequipment including but not limited to broadcast spreaders, dropspreaders and/or hand distribution means. The application of biocharaggregate particles can be used for trees, row crops, vines, turfgrasses, potted plants, flowering plants, annuals, perennials,evergreens and seedlings. The biochar aggregate particles may also beapplied to animal pens, bedding, and/or other areas where animal wasteis present to reduce odor and emission of unpleasant or undesirablevapors. Furthermore it may be applied to compost piles to reduce odor,emissions, and temperature or even to areas where fertilizer orpesticide runoff is occurring to slow or inhibit leaching and runoff.The aggregates may also be integrated with animal feed and/or othersubstances beneficial to animal health, either whole (biochar pelletsmixed with separate feed pellets to form an aggregate, for example), orwith animal feed or other beneficial substances mixed into the biocharslurry or paste prior to extrusion. Biochar aggregate particles may beincorporated into or around the root zone of a plant. As most trees,rows, and specialty crops extract greater than 90% of their water fromthe first twenty-four inches below the soil surface, the aboveapplications will generally be effective incorporating the biochararound the root zone from the top surface of the soil and up to a depthof 24″ below the top surface of the soil, depending on the plant typeand species, or alternatively, within a 24″ radius surrounding the rootsregardless of root depth or proximity from the top surface of the soil.When the plant roots are closer to the surface, the incorporation of thebiochar within the top 2-6″ inches of the soil surface may also beeffective. Greater depths are more beneficial for plants having largerroot zones, such as trees.

Biochar aggregates are particularly useful, when they will be put intoan application that requires mixing with other solid granular products.This is because the aggregates can be designed and created to be similarin shape, size, or density to that which it will be mixed with. When theaggregates are physically similar to the material particles they will bemixed with then the final mixture will stay more uniformly mixed andhave better flow properties. When a specific rate of each material inthe mixture is needed, say in agriculture or animal feed, then a uniformmixture is critical to ensure the soil or animal consistently gets thecorrect rate.

K. Biochars for Use in Composting

In addition to the use of treated biochar in connection with agricultureand animal applications for human consumption, treated biochar can alsobe used throughout the world, in numerous composting applications. Thebiochar used in composting applications can be all treated biochar, inaccordance with the treatment processes set forth above, or may be mixedwith raw, untreated biochar.

FIG. 42 is a diagram illustrating one example of the work flow for acommercial food composting operation. As illustrated in the diagram,compost material is first dropped at a weigh station, where clients arepaid various rates for the compost materials. The materials thenreleased to a tipping floor and segmented by types. Green waste/woodsare cleaned and ground down on the production floor. Foods are slowlyreceived and stored. Screening of green waste/woods creates varioussized inputs. Stored food is blended with green waste/woods viascreening to remove inerts from food.

When composted using covered aerated static piles (“CASP”), piles of thematerials are placed over porous pipes. Tarps are laid over the pipes.Negative pressure aerates the piles and pulls odor into a biofilter. TheCASPs run for approximately 30 days. When the piles are composted usingwoodrow (mechanical turning), the piles are kept in the woodrow forapproximately 15 days.

Biochar can be applied to composting environments to allow for thecontrol of temperature, moisture, pH levels, odors and bacterialcultures. As illustrated below, applying biochar in compostingenvironments has been shown to significantly reduce water loss, controltemperatures, reduce odors and control acidic pH issues. The presenttreatment processes for biochar allow for the capability ofcustom-manufacturing biochar for use in composting for a particularclimate, environment, geographical area, or by more preciselycontrolling key characteristics of the biochar.

The method of the present invention for applying biochar to compostsincludes blending low, affordable rates of treated biochar (1%-5% v/v)with feedstock high in food residuals (40% v/v). Treated biochar mayalso be blended with other materials, such as raw and/or processedbiochar, processed differently than the treatment processes describedabove, and with compost having other compositions than feedstock high infood residuals. Blending various rates of treated biochar, by itself, orwith raw and/or processed biochar, in various composting environmentsmay produce different desired results.

One of the recurring problems in composting environments is to controlthe acidity levels and the lowering of pH in the compost. Food residualscontain high levels of organic acids like lactic acid. Low pH shifts themicrobial community to more acid tolerant microbes that stimulate afeedback loop wherein lactobacilli produce more lactic acid. FIG. 43 isa chart showing the pH of compost as the percent of lactic acidincreases. As illustrated in FIG. 43, the more lactic acid by percent,the lower the pH in compost. FIG. 43 shows the general pH of compostmaterials, before commencing the composting process. FIG. 44demonstrates how pH is influenced in compost when mixing green wastes,woods and foods. As illustrated, the addition of foods and woods tocompost lower the pH of the compost. Green waste provides the highestpH, while the combination of foods, green waste and wood, produce thelowest pH.

In composting, different microbial communities degrade the organic acidsto raise the pH. Generally, the starting point for feedstock compostingis a pH of ≥6.0. In CASP methods, feedstock compost may remain acidic toa pH of ≤5.0. Acidic compost is not ideal for plant nutrient uptake orother uses of the compost. Raising the pH in the compost is desired fora number of reasons.

Adding treated biochar to compost has been shown to increase aerationand lower and/or control the temperatures in the compost, leading tohigher, less acidic pH levels. Lower temperatures are critical in theearly stages of composting to stimulate the mesophilic (“cool-loving”)microbes to outcompete the thermophilic (“heat-loving”) microbesinherent to food residuals. Lactic acid bacteria are thermophiles thatgenerally reduce the pH levels in compost. Adding treated biochar tocompost appears to reduce lactic acid bacteria and generally increasethe pH levels in compost. Despite lower temperatures, pathogen reductionstill occurs. These reduced composting temperatures also means less airand water will be required.

FIG. 45 is a chart showing the impact on composting temperatures when 1%and 3% treated biochar are added to the compost (control). The controlrepresents the compost with 0% added biochar. As shown by FIG. 45,adding treated biochar to compost in a windrow environment generallydecreases the temperature in the compost. It was shown that adding 1-3%treated biochar to the compost in a windrow environment generallylowered the temperature in the compost between 5-20° F.

FIG. 46 is a chart showing the decrease of lactic acid production incompost by adding treated biochar. As shown by FIG. 46, adding treatedbiochar to compost in a windrow environment generally decreases thelactic acid in the compost. The addition of 1% treated biochar in thecompost reduced the lactic acid by 0.5-0.6% DM and the addition of 3%treated biochar in the compost reduced the lactic acid by as much as1.0-1.1% DM. The control compost is represented by 0% added treatedbiochar.

FIG. 47 is a chart showing the increase in pH in compost by addingtreated biochar. As shown by FIG. 47, adding treated biochar to compostin a windrow environment generally increases the pH level in thecompost. The addition of 1% treated biochar in the compost increased thebasicity from between 4.7-4.8 pH to approximately 5.1 pH. The additionof 3% treated biochar in the compost increased the basicity from between4.7-4.8 pH to approximately 5.3 pH. The control compost is representedby 0% added treated biochar.

FIG. 48 is a chart showing the increase in oxygen levels in compost byadding treated biochar. As shown by FIG. 48, adding treated biochar tocompost in a windrow environment generally increases the oxygen level inthe compost. The addition of 1% treated biochar in the compost increasedthe oxygen level from approximately 18.4% to approximately 19.8%. Thecontrol compost is represented by 0% added treated biochar. Theincreased oxygen levels show the increased aeration in the compost andmay explain the lowered temperatures also observed.

FIGS. 49 and 50 show the impact of the addition of both raw and treatedbiochar in a CASP compost environment to volatile fatty acids (VFAs) andammonia (NH₃) levels, respectively. When comparing raw biochar totreated biochar in CASP environments, it was generally shown that rawbiochar has no effect on volatile fatty acids (VFAs) and increases NH₃levels. Treated biochar on the other hand was shown to reduce both VFAsand NH₃ levels and indicative of reducing air emissions. VFAs and NH₃levels are known to be odor indicating compounds. Reducing the amount ofVFAs and NH₃ levels in the compost should indicate a reduction in theodor produced by the compost. Additionally, if NH₃ levels are reduced,then the nitrogen is more likely staying in the form of ammonium (NH4)and eventually turning into nitrates, which improves the quality of theresulting compost product.

As shown by FIG. 49, adding treated biochar to compost in a CASPenvironment generally decreases VFAs while the addition of raw biocharhas no visible effect. The control compost has 0% added biochar. Asshown by FIG. 50, adding treated biochar to compost in a CASPenvironment generally decreases NH₃ while the addition of raw biocarbonincreases NH₃. The control compost has 0% added biochar.

FIG. 51 is a chart showing the impact on volatile organic compounds(“VOC”) by adding treated and raw biochar to CASP compost. As shown, theaddition of raw or treated biochar has variable effects on VOCs and canincrease or decrease volatile organic compounds. The measurements weretaken from negative pressure system of compost from a CASP environmenttapped into a summa canister to capture gases generated by the compost.The addition of treated biochar to compost, compared to the controlcompost (0% biochar added), decreased the percentage of methyl-iso-butylketone (MBK), ethanol and methanol, while it increased the percentage of2-propanol, propene, 2-butanone and acetone. The addition of rawbiochar, compared to the control compost, decreased the percentage ofpropene, 2-butanone, acetone and methanol, while it increased thepercentage of MBK and 2-propanol.

FIG. 52 is a chart shows a test of evaporative water loss from controlcompost (Control 100) against blended treatments with raw or processedbiochars at 1, 3 and 5% by volume. Treated biochar at 1 or 3%outperformed raw treatments by as much as 10%. Treated biochar added tocontrol compost at 3% v/v showed a dramatic 17.5% reduction inevaporative loss. The control compost in FIG. 52 is without raw and/ortreated biochar. As shown, the evaporative loss of water in compostdecreased as much as 10% if the compost is mixed with 1-3% processedbiochar. Mixing the compost with 3% treated biochar has shown tomaintain moisture levels in the compost essential for a climate similarto California.

FIG. 53 is a chart showing the effect that the addition of treatedbiochar has on percent mass water loss in a CASP compost environment.Mass was determined by pile volume and bulk density. As shown in FIG.53, adding % treated biochar to the piles of control compost reduced thewater mass loss by 10%. The control compost in FIG. 53 is without rawand/or processed biochar.

All biochar treatments of compost have shown reductions in water lossand mixing various levels of treated biochar into the compost can assistto control essential moisture levels for various climates and assist inoptimizing the composting process. Similar effects are seen windrowcompost environments. As treated biochar controls the pile temperatures(see FIG. 45), despite the lower temperatures pathogen reduction stilloccurs. Lower pile temperature can reduce water demand up to 1,000gallons of water added every 3-4 days.

FIGS. 54, 55 and 56 all demonstrate the impact of inoculating thebiochar with specialized microbes. In all cases, the compost includes2.6% biochar. The biochar added to the control is raw biochar. Thebiochar B2XNA and B2XA are inoculated with bacillus. Bacillus spp. waschosen for their ability to form endospores that allow the microbes tosurvive harsh temperature found during composting. Relative PercentAbundance of Bacillus spp. is as follows: Bacillus licheniformis (25%);Bacillus szutsauensis (5%); Bacillus amyloliquefaciens (15%); Bacillussubtilis (18%); Bacillus velezensis (26%); and Bacillus pumilus (33%).The types of Bacillus used were selected for the following purposes:nutrient cycling (B. licheniformis and B. subtilis), nitrogen fixation(B. pumilus), biocontrol of plant pathogens (B. velezensis and B.subtilis), and plant growth promotion (B. pumilus and B. subtilis). B2XAwas pH adjusted, whereas B2XNA was not pH adjusted. B4XA is inoculatedwith twice as much bacillus as the B2XA and was also pH adjusted.

FIG. 54 is a chart showing in impact of the addition of the inoculatedbiochar to compost on microbial abundance. FIG. 55 is a chart showing inimpact of the addition of the inoculated biochar to compost on VOCs.FIG. 56 is a chart showing in impact of the addition of the inoculatedbiochar to compost on NH₃.

FIG. 54 shows that compost piles having 2.6% inoculated biochar hadelevated populations of gram positive bacteria. As illustrated, compostpiles mixed with biochar inoculated with bacteria are shown to haveelevated populations of gram positive bacteria. This suggests thatthermotolerant endospore forming bacterial inoculated into biocarbon cansurvive native competition in composting systems and may have a positiveeffect on the composting process.

Regarding FIG. 55, it was generally determined that inoculated biocarbondecreases VOC levels. However, inoculated biochar, B4XA, treatment ofbiocarbon increased the VOC levels, possibly due to elevated bacilluspopulations.

Regarding FIG. 56, it was generally determined that inoculated biocarbondecreases NH₃ levels.

In general, in the application of biochar to compost, it was shown thattreated biochar is able to raise the pH levels in composting with foodwaste, improves aeration, lowers temperature of compost piles, and canreduce odor indicating compounds like ammonia, VFAs and other volatileorganics. Compared to raw biochar, treated biochar outperforms with thecontrol of most of the odor indicating compounds and, at lower doses,with the ability to reduce evaporative loss. Treated biochar helpsreduce overall water loss that occurs during composting and helps reducewater inputs regarding temperature control.

In addition to the composting benefits seen by adding treated biochar,the value of the resulting compost is also increased. Since the treatedbiochar helped retain nitrogen during the composting (as seen by reducedNH₃), the compost itself will have higher nutrients when applied inagriculture usage. Also, the treated biochar remains in the compost andcontinues to display the benefits outlined in this invention, includingbut not limited to water and nutrient retention. Thus when the resultingcompost is used in agriculture the compost will show similar improvementtrends as when treated biochar itself is applied.

In another implementation or this invention, treated biochar could beadded directly to animal bedding to control odors. Then once used, thebedding could be recycled via composting and still get the benefits ofthe treated biochar in composting. And finally the resulting compostwhich still has treated biochar could be used in agriculture and stillcontinue to provide additional benefits to plants as well.

L. Animal Applications

Generally, treated biochar of the present inventions can be used withnumerous animal species, large and small scale farming, and in a varietyof animal management applications and systems, and combinations andvariations of these. In fact, this particular solution provides thecapability to custom-manufacture biochar for a particular species,physiology, nutritional need, pathogen susceptibility, illness,environment, geographical area or other application by more preciselycontrolling key characteristics.

The fundamental benefit of treated biochar use in animal applications isthe fact that deleterious characteristics can be adjusted and toxicmaterials left over from the biomass and its pyrolysis can be removed.For example, pH can be adjusted, and undesirable ash, inorganiccompounds, toxins or heavy metals, and organic compounds such as acids,esters, ethers, ketones, alcohols, sugars, phenyls, alkanes, alkenes,phenols, polychlorinated biphenyls or poly or mono aromatichydrocarbons, can be removed. As described previously, one major concernwith charcoals or raw biochars used in animal applications is thepotential for dioxins which are released from combustion processes andare an example of toxic material that the treatment of the presentinvention can remove. Thus, a treated biochar can be used in animalapplications where ingestion may be possible such as bedding, orspecifically as a feed additive, whether it be for general purpose suchas color, manure odor control, or roughage replacement or as a technicaladditive as a binding agent or carrier as it can be made without toxins,specifically dioxins, consistently with various feedstocks and variouspyrolysis methods without risk of harm to the animals or humans thatconsume the animal products/meat from said animals.

Through the use of detoxified treated biochars, the other benefits ofbiochar qualities can be realized in applications related to the care,maintenance and feeding of animals. These benefits can include increasein animals' uptake of foodstuffs and the energy contained within them;reduction in the amount of nutrients lost into excrement and manure;detoxification of the animal and enrichment of the beneficial microbesin the digestive track that are key to maintaining an animal'smetabolism and helping it to resist dangerous pathogens; reduction inmethane production; better odor control of stalls, pens, cages, lagoonsand other animal enclosures; and any combination and variation of theseand other benefits. The results are increased growth rates for animalsconsuming treated biochar, as well as better overall health of theanimals that consume it, greater efficiencies in animal care andmaintenance, and improved odor. As an additional benefit, manureproduced by an animal that consumes biochar contains biochar, makingthis manure better for agricultural purposes than ordinary manure.

For animal applications, in the same way that biochars are known to bindorganic contaminants in soil environments due to hydrophobic-hydrophobicinteractions, treated biochar may bind organic toxins as they passthrough an animal's digestive system, for example, when cattle aresuffering from botulism or diarrhea. Another toxin binding applicationcould be with commercial farm pollinating bee hives. Bee species havebeen on the decline in the US and this year, the first species of bee inthe continental US was placed on the endangered species list. Beespecies' decline appears to be in part due to fungicides, andinsecticides, including neonicotinoids, leading to bees becoming moresusceptible to disease. See Pettis et al., Crop Pollination ExposesHoney Bees to Pesticides Which Alters Their Susceptibility to the GutPathogen Nosema ceranae, PLOS, Jul. 24, 2013(http://journals.plos.org/plosone/article?id=10.1371/journal.pone.0070182).

Adding small particle treated biochar to a commercial hive feed patty,which generally consist of sugar and protein and may have additionalvitamins or probiotics, may allow the insects to ingest said treatedbiochar and allow for it to help bind the pesticide toxins and helplessen their sub-lethal effects to keep the bees more resistant topathogens even when they have been and continue to be exposed to thesepesticides.

In another example, biochars were shown to absorb Cadmium, a heavymetal, but the absorption capacity was depended on the biocharproperties including the biomass feedstock type. FIG. 57 is chartillustrating biochar capacity to absorb Cadmium. Thus a specific treatedbiochar formulation can be developed for each toxin binding animalapplication to ensure optimum results for the specific toxin(s) ofconcern.

Another application is to use the treated biochar as bedding in order toreduce odors, absorb ammonia, and absorb toxins and thus lead to anenvironment that will lead to healthier animals and also lead to abetter secondary product of quality manure by reduced nutrient leaching.A bedding trial was conducted with broiler chickens. After decaking thehouses, the test houses had treated biochar spread evenly over theentire house at various rates while one was left as a control. The flockproduced over the two sets of trials was above normal. After the firsttrial, manure samples were tested from each house for nutrient contentand estimated 1^(st) year availability of said nutrients. The estimatedmanure value was then calculated off of the estimated 1^(st) yearavailability. Results showed higher value for the bedding with treatedbiochar, as seen in table below:

1^(st) Year Availability (lbs/ton) Control With Treated Biochar Total N37 35 P (P2O5) 31 34 K (K2O) 56 61 Total Est. Value $56.40 $58.90

As was discussed previously, mixing treated biochar in while compostingcan reduce odors, these same mechanisms can be used to reduce odors whentreated biochar is mixed with animal bedding, manure, swine lagoons,etc.

Typically, the prior art teaches mixing raw biochar with animal feedwithout ‘precharging’ with nutrients, microbes, etc. Throughimpregnation of the biochar particles, one can achieve a predeterminedand controllable amount of a particular nutrient, medication, foodstuff,microbial community, etc. being ingested by the animal. Once in therumen, data indicates that these infused additives will also be releasedmore slowly over time, yielding yet another benefit over additives mixeddirectly into the feed. This integration of a beneficial additive with abiochar particle and biochar batches provides the ability to havecontrolled addition, use and release of the additive or additives. Thisintegration may further enhances, promotes and facilitate animal growthand health, aid in digestion and digestibility of food, improvementhygiene, increase intestinal health, reduces the amount of nutrientslost into excrement and manure and reduces methane discharge.

Enhancing treated biochar with an additive, including infusing liquidsinto the pores of biochar, can provide additional benefits in animalapplications, by making it an effective delivery mechanism forbeneficial nutrients, pharmaceuticals, enzymes, microbes, or othersubstances. Additionally a sensory enhancer, such as a smell or flavor(e.g. salt), could be infused to increase the animal's desire to ingestsaid biochar.

The additive may include, but not be limited to, water, water solutionsof salts, inorganic and organic liquids of different polarities, liquidorganic compounds or combinations of organic compounds and solvents,vitamins, supplements and/or medications, nutrients, minerals, oils,amino acids, fatty acids, supercritical liquids, growth promotants,proteins and enzymes, phytogenics, carbohydrates, antimicrobialadditives and sensory additives (e.g. flavor enhancers salt orsweeteners or smell enhancers), among others, to provide nutrition,promote the overall health of the animal, and increase the animal'sdesire to ingest said biochar. Vitamins, supplements, minerals,nutritional and/or medications may be used to prevent, treat or cureanimal illnesses and diseases and/or control the nutritional value ofthe animals overall diet.

For example, dietary supplementation with certain nutrients (e.g.,arginine, glutamine, zinc, and conjugated linoleic acid) can regulategene expression and key metabolic pathways to improve fertility,pregnancy outcome, immune function, neonatal survival and growth, feedefficiency, and meat quality. Such additives in the biochar can helpprovide the proper balance of protein, energy, vitamins andnutritionally important minerals in animal diets. Additionally, forpoultry, the additive may include, for example, coccidiostats and/orhistomonostats, which are both shown to control the health of thepoultry. The present invention can be used to help correct deficienciesin basal diets (e.g., corn- and soybean meal-based diets for swine; milkreplacers for calves and lambs; and available forage for ruminants).

The treated biochar can also have a microbial community infused in itspores (macro-, meso-, and combinations and variations of these), on itspore surfaces, embedded in it, located on its surface, and combinationsand variations of these. The microbial community can have severaldifferent types, e.g., species, of biologics, such as different types ofbacteria or fungi, or it may have only a single type. A primary purpose,among many purposes, in selecting the microbial population is lookingtoward a population that will promote animal health either directly orthrough interactions with other microbes in the animals digestive tract.These types of beneficial microbes are essential to a functionalgastrointestinal tract and immune system in many types of animals,serving many functional roles, including degradation of ingesta,pathogen exclusion, production of short-chain fatty acids, compounddetoxification, vitamin supplementation, and immunodevelopment.Beneficial bacteria include Lactobacillus acidophilus LA1 (whichdecreases adhesion of diarrheagenic Escherichia coli to Caco-2 cells by85% and prevents invasion of the same cells by E. coli (95%), Yersiniapseudo-tuberculosis (64%) and Salmonella enterica serovar Typhimurium)and Lactobacillus rhamnosus GG to prevent E. coli O157:H7-inducedlesions in Caco-2 cells.

Further, biochar may be impregnated with probiotic bacteria to treatdiseases in farm-raised fish. Infectious diseases pose one of the mostsignificant threats to successful aquaculture. The maintenance of largenumbers of fish crowded together in a small area provides an environmentconducive for the development and spread of infectious diseases. In thiscrowded, relatively unnatural environment, fish are stressed and moresusceptible to disease. Moreover, the water environment, and limitedwater flow, facilitates the spread of pathogens within crowdedpopulations. There is thus an urgent need in aquaculture to developmicrobial control strategies, since disease outbreaks are recognized asimportant constraints to aquaculture production and trade and since thedevelopment of antibiotic resistance has become a matter of growingconcern. One alternative disease control relies on the use of probioticbacteria as microbial control agents. Another implementation of theinvention therefore involves the impregnation of biochar for consumptionby aquatic animals as a treatment or preventative for disease.

Additionally, biochar may be infused with bacteria which prove helpfulin methane reduction. An example of this is to infuse the biochar withmethanotrophic bacteria (bacteria which are able to metabolize methaneas a source of carbon and energy). Bacteria which metabolize methane areuseful in two regards—they can reduce the environmental methaneemissions from the rumen and they (the bacteria) also serve as nutritionfor the animal itself, leading to increased weight gain. Infusingbiocarbon with microbes such as these can lead to methane reduction incattle applications that exceeds the methane reduction of solelyuntreated biochar itself.

Additive infused biochars may be mixed with the animals regular feeds ormay be included within a salt or mineral block and made available foranimals to self-feed or self-administer the additives.

While this application focuses mainly on applications of infusedbiochars in connection with farm-raised animals, those skilled in theart will also recognize that the invention could also be applied moregenerally for veterinary purposes for many types of animals other thanlivestock, poultry, fish or horses, including pets, as well as in a widevariety of environments and contexts, for example, for zoo or aquariumanimals or for other penned or caged animals, insects such as bees, orfor wild animals.

Furthermore, the treated or additive infused biochar can be sized,agglomerated, or suspended in solution to optimize its use in a specificanimal application. For example, if using as a feed additive withsmaller animals or very young animals, small particles will be requiredand being able to suspend these small particles in a solution will makefor an easier application.

In addition, if the treated or additive infused biochar is being used todeliver its specific benefit in a targeted location in the animals'digestive tract, it can be mixed with an additive or coated to allow fora slower release or a targeted release in said location. So, for exampleif the additive or biochar is being targeted for use in the intestinesor after rumens a specific coating substance and thickness can be chosenso as to degrade at the required specified rate leading to the biocharor additive being available after the stomach or rumens. This could bespecifically useful for getting beneficial microbes to targeted organsin the digestive tract. If the microbe is infused into the pores to asignificant depth of at least approximately 10 to 20 microns, then boththe biochar structure itself and a coating could be used to protect themicrobe through harsh conditions, such as stomach acid, prior to gettingto the targeted organ location.

Treated biochar and additive infused treated biochar can be used inpromoting growth and health in livestock (dairy and beef cattle, sheep,goats and swine); poultry; farm-raised wild animals (e.g. bison, deerand elk); farm-raised fish and other aquatic animals; horses and othermembers of the horse family; for controlling levels of certainpathogens, e.g. salmonella in poultry; for veterinary uses, such asdelivery systems for medications, supplements and/or vitamins; formaintenance and welfare of zoo animals or other caged, penned orcontained animals; for pets; for zoos and aquaria; for wild animals; forinsects, such as bees, and for combinations and variations of these.

Treated biochars and practices and methods provide for healthieranimals, increase food intake efficiency, promote better digestion andreduce methane emissions, and combinations and variations of these, andother features that relate to the increased holding, retention and timedischarge features of the present biochars and processes.

Treated biochar may also be used in other applications, for example,such mixing with manure in holding ponds to potentially reduce gaseousnitrogen losses, soil remediation (for example absorption and capture ofpesticide, contaminates, heavy metals, or other undesirable,disadvantageous soil components), ground water remediation, otherbioremediations, storm water runoff remediation, mine remediation andmercury remediation.

In summary, the treatment processes of the present information may beused to clean the pores of the biochar, ridding the pores of dioxins orother detrimental substances, or infiltrating the pores of biochar witha variety of substances, for a number of purposes, including but notlimited to, infiltrating the pores of biochar with nutrients, vitamins,drugs, microbes, and/or other supplements, or a combination of any ofthe foregoing, for consumption by animals. The treated biochar may alsobe applied to animal pens, bedding, and/or other areas where animalwaste is present to reduce odor and emission of unpleasant orundesirable vapors. Furthermore it may be applied to compost piles toreduce odor, emissions, and temperature to enable the use of the foodwaste and animal feed in composting. Biochar can also be applied toareas where fertilizer or pesticide runoff is occurring to slow orinhibit leaching and runoff. The biochar may also be treated withadditives which make it easier to dispense or apply, such as non-toxicoils, anti-clumping/binding additives, surface drying agents, or othermaterials.

While the above teaches a treatment process for biochar that increasesthe amount of additives that can be retained within the pores of thebiochar, it is within the scope of the present invention to contact rawor treated biochar with additives (e.g. by submersion) for purposes ofcreating a delivery system for additives useful for animal health andconsumption.

As set forth above, the treated biochar of the present invention may beused in various agriculture activities, as well as other activities andin other fields. Additionally, the treated biochar may be used, forexample, with: farming systems and technologies, operations oractivities that may be developed in the future; and with such existingsystems, operations or activities which may be modified, in part, basedon the teachings of this specification. Further, the various treatedbiochar and treatment processes set forth in this specification may beused with each other in different and various combinations. Thus, forexample, the processes and resulting biochar compositions provided inthe various examples provided in this specification may be used witheach other; and the scope of protection afforded the present inventionsshould not be limited to any particular example, process, configuration,application or arrangement that is set forth in a particular example orfigure.

Although this specification focuses on applications related to themaintenance, care, feeding and health of animals, it should beunderstood that the materials, compositions, structures, apparatus,methods, and systems, taught and disclosed herein, may have applicationsand uses for many other activities in addition to agriculture forexample, as filters, additives, and in remediation activities, amongother things.

It is understood that one or more of these may be preferred for oneapplication, and another of these may be preferred for a differentapplication. Thus, these are only a general list of preferred featuresand are not required, necessary and may not be preferred in allapplications and uses.

It is noted that there is no requirement to provide or address thetheory underlying the novel and groundbreaking functionality,performance or other beneficial features and properties that are thesubject of, or associated with, implementations of the presentinventions. Nevertheless, to the extent that various theories areprovided in this specification it is done to further advance the art inthis important area. These theories put forth in this specification,unless expressly stated otherwise, in no way limit, restrict or narrowthe scope of protection to be afforded the claimed inventions. Thesetheories many not be required or practiced to utilize the presentinventions. It is further understood that the present inventions maylead to new, and heretofore unknown theories to explain thefunctionality, performance or other beneficial features and propertiesthat are the subject of, or associated with, embodiments of the methods,articles, materials, and devices of the present inventions; and suchlater developed theories shall not limit the scope of protectionafforded the present inventions.

Those skilled in the art will recognize that there are other methodsthat may be used to treat biochar in a manner that forces the infusionof liquids into the pores of the biochar without departing from thescope of the invention. The foregoing description of implementations hasbeen presented for purposes of illustration and description. It is notexhaustive and does not limit the claimed inventions to the precise formdisclosed. Modifications and variations are possible in light of theabove description or may be acquired from practicing the invention. Theclaims and their equivalents define the scope of the invention.

I claim:
 1. An aggregate particle that is less than 5 mm and iscomprised of biochar fines that are less than 1 mm and a binding agent.2. The aggregate particle of claim 1 where the binding agent is clay. 3.The aggregate particle of claim 1 where the binding agent is a starch.4. The aggregate particle of claim 1 where the binding agent includes alignin, a polymer and/or a lipid.
 5. The aggregate particle of claim 1,where the biochar fines have been treated with a surfactant solution. 6.The aggregate particle of claim 1, where the biochar fines have beentreated using a vacuum.
 7. The aggregate particle of claim 1, where thebiochar fines have been treated using ultrasonics.
 8. The aggregateparticle of claim 1, where the biochar fines have been treated byinfusing a liquid into the pores of the biochar fines.
 9. The aggregateparticle of claim 8, where the biochar fines have been infused with aliquid or vapor additive.
 10. The aggregate particle of claim 9, wherethe additive includes a selection from one or more of the following: afertilizer, a nutrient, a vitamin, a supplement, or a medication. 11.The aggregate particle of claim 9, where the additive includes a microbeor microbial spore.
 12. The aggregate particle of claim 9, where theadditive includes a fungicide, insecticide, or nematicide.
 13. Theaggregate particle of claim 9, where the additive includes a planthormone, secondary signal activators, or signaling agent.
 14. Theaggregate particle of claim 1, where the biochar fines have been treatedwith a pH adjusting solution.
 15. The biochar aggregate particle ofclaim 1, where 95% of the biochar fines are between 0.1 and 0.5 mm inequivalent diameter.
 16. An aggregate particle that is less than 5 mmand is comprised of biochar fines that are less than 1 mm, a bindingagent, and an additive.
 17. The aggregated particular of claim 16 whereadditive includes is selection from one or more of the following: afertilizer, a nutrient, a vitamin, a supplement, a medication, anutrient, a vitamin, a supplement, medication, a microbe, a microbialspore, a fungicide, an insecticide, a nematicide, a plant hormone,secondary signal activators or signaling agent.
 18. The aggregateparticle of claim 17, where the fertilizer is ammonium nitrate, ammoniumsulfate, monoammonium phosphate, ammonium polyphosphate, Cal-Matfertilizer, and/or a micronutrient fertilizer.
 19. The aggregateparticle of claim 17, where the nutrient is nitrogen, phosphorus,potassium, calcium, magnesium, sulfur, boron, zinc, iron, manganese,molybdenum, copper and/or chloride.
 20. An aggregate particle that isless than 5 mm and is comprised of biochar fines that are less than 1mm, surfactant, and a binding agent.
 21. The aggregate particle of claim20, where the surfactant is a nonionic type surfactant
 22. The aggregateparticle of claim 20, where the surfactant is an anionic type surfactant23. The aggregate particle of claim 20, where the surfactant is acationic type surfactant
 24. The aggregate particle of claim 20, wherethe surfactant is an amphoteric type surfactant.